Compounds for a controlled release of active perfuming molecules

ABSTRACT

The present invention relates to the field of perfumery. More particularly, it concerns compounds comprising at least one β-thio carbonyl or nitrile moiety capable of liberating an active molecule selected from an α,β-unsaturated ketone, aldehyde or nitrile. The present invention concerns also the use of said compounds in perfumery as well as the perfuming compositions or perfumed articles comprising the invention&#39;s compounds. (I) wherein: a) m represents an integer from 1 to 6; b) Pro represents a hydrogen atom or a group susceptible of generating an odoriferous α,β-unsaturated ketone, aldehyde or nitrile and is represented by the formulae (II) or (II′) in which the wavy line indicates the location of the bond between said Pro and the sulfur atom S; and at least one of the Pro groups is of the formula (II) or (II′).

TECHNICAL FIELD

The present invention relates to the field of perfumery. Moreparticularly, it concerns compounds comprising at least one β-thiocarbonyl or nitrile moiety capable of liberating an active molecule suchas, for example, an α,β-unsaturated ketone, aldehyde or nitrile. Thepresent invention concerns also the use of said compounds in perfumeryas well as the perfuming compositions or perfumed articles comprisingthe invention's compounds.

PRIOR ART

The perfume industry has a particular interest for compounds which arecapable of prolonging the effect of active ingredients over a certainperiod of time, for example in order to overcome the problemsencountered when using perfuming ingredients which are too volatile orhave a poor substantivity. These compounds can be used in variousapplications, as for example in fine or functional perfumery. Thewashing of textiles is a particular field in which there is a constantquest to enable the effect of active substances, in particular perfumes,to be effective for a certain period of time after washing and drying.Indeed, many substances having fragrances which are particularlysuitable for this type of application are, in fact, known to lacktenacity on laundry, or do not remain on the laundry when rinsed, withthe result that their perfuming effect is experienced only briefly andnot very intensely. Given the importance of this type of application inthe perfume industry, research in this field has been sustained, inparticular with the aim of finding new, and more effective solutions tothe aforementioned problems.

Amongst the compounds of the present invention, only a few are knownfrom the prior art. Said known compounds are phenylmethyl2-[[1-methyl-1-(4-methyl-2-oxocyclohexyl)-ethyl]thio]-acetate (mentionedin CAS but no reference reported), methyl2-[[[(1S,2R,5R)-6,6-dimethyl-3-oxobicyclo[3.1.1]hept-2-yl]methyl]thio]-acetate(E. Mountaudon et al. in Helv. Chim. Acta, 2000, 83, 616), ethyl/methyl2-((3-oxo-1,3-diphenylpropyl)thio)acetate and methyl2-[(3-oxo-1-phenylbutyl)thio]-acetate (X. Feng et al. in Angew. Chem.Int. Ed., 2010, 49, 4290),2-((2-methyl-3-oxo-5-(prop-1-en-2-yl)cyclohexyl)thio)acetic acid andethyl 2-((2-methyl-3-oxo-5-(prop-1-en-2-yl)cyclohexyl)thio)acetate (E.V. Sirazieva et al. in Chem. Nat. Compd., 2006, 42, 693),3-phenyl-2-propenenitrile (WO 03/029188). Other compounds similar tothose of formula (I) have been described but they are not able torelease a perfuming ingredient:2-allyl-3-methyl-4-carboxymethylthio-2-cyclopentenone (U.S. Pat. No.4,665,174), 14-O-[(cyclohexanone-3(R/S)-yl)-sulfanylacetyl]-mutilin (WO2007/014409), methyl2-(((1-oxo-1,2,3,4-tetrahydronaphthalen-2-yl)(phenyl)methyl)thio)acetateand methyl2-(((1-oxo-2,3-dihydro-1H-inden-2-yl)(phenyl)methyl)thio)acetate(supporting information of X. Feng et al. in Angew. Chem. Int. Ed.,2010, 49, 4290).

However, all the compounds mentioned above have been used as syntheticintermediates and not as perfuming ingredients. Moreover, in thedocuments mentioned to hereinabove, there is no mention or suggestion ofthe potential use of said compounds as perfuming ingredients and morespecifically of the use of said compounds to control the release ofactive, e.g. odoriferous, molecules.

Some β-thio carbonyls are a known class of compound useful as perfumeryingredient (see WO 03/049666) which describe inter alia3-(dodecylthio)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone.However, WO 03/049666 does not anticipate that the present compoundsprovided such increase performance.

DESCRIPTION OF THE INVENTION

We have, surprisingly, discovered the existence of compounds comprisingat least one β-thio carbonyl or nitrile moiety and which are capable ofliberating an active molecule. As “active molecule” we mean here anymolecule capable of bringing an odor benefit or effect into itssurrounding environment, and in particular an odoriferous molecule, i.e.a perfuming ingredient, such as an α,β-unsaturated ketone, aldehyde ornitrile. The invention's compounds are thus valuable perfumingingredients.

Therefore a first aspect of the present invention concerns the compoundsof formula

wherein:

-   a) m represents an integer from 1 to 6;-   b) Pro represents a hydrogen atom or a group susceptible of    generating an odoriferous α,β-unsaturated ketone, aldehyde or    nitrile and is represented by the formulae

-   -   in which the wavy line indicates the location of the bond        between said Pro and the sulfur atom S;    -   R¹ represents a hydrogen atom, a C₁ to C₁₅ linear, cyclic or        branched alkyl, alkenyl or alkadienyl group, optionally        substituted by C₁ to C₄ alkyl groups; and    -   R², R³ and R⁴ represent a hydrogen atom, a C₆₋₉ aromatic group        or a C₁ to C₁₅ linear, cyclic or branched alkyl, alkenyl or        alkadienyl group, said R², R³ and R⁴ being optionally        substituted by C₁ to C₄ alkyl groups; or two, or three, of the        groups R¹ to R⁴ are bonded together to form a saturated or        unsaturated ring having 6 to 20 carbon atoms and including the        carbon atom to which said R¹, R², R³ or R⁴ groups are bonded,        this ring being optionally substituted by C₁₋₈ linear, branched        or cyclic alkyl or alkenyl groups;    -   and with the proviso that at least one of the Pro groups is of        the formula (II) or (II′) as defined hereinabove;

-   c) X represents an oxygen atom or a NR⁵ group, R⁵ being a hydrogen    atom or a C₁₋₁₀ hydrocarbon group;    -   d) R represents a divalent linear, branched or cyclic        hydrocarbon group having from 1 to 6 carbon atoms optionally        comprising a carboxylic acid or an alkaline carboxylate group;        and    -   e) G represents a hydrogen atom, an alkaline metal cation, an        ammonium cation, or a multivalent C₁₋₂₂ hydrocarbon group (i.e.        having a m valence) optionally comprising one silicium atom        and/or from 1 or 2 functional groups selected from the group        consisting of ether, alcohol, ester, ketone, quaternary amine or        amine, or represents mono- or divalent C₄₋₃₀ hydrocarbon group        comprising from 2 to 15 ether functional groups.

As “α,β-unsaturated ketone, aldehyde or nitrile”, expression used in thedefinition of Pro, we mean here an α,β-unsaturated ketone, aldehyde ornitrile which is recognized by a person skilled in the art as being usedin perfumery as perfuming ingredient. It is understood that said“odoriferous α,β-unsaturated ketone, aldehyde or nitrile” in order to bequalified as perfuming ingredient must be able to impart or modify in apositive or pleasant way the odor of a composition, and not just have anodor.

In general, said odoriferous α,β-unsaturated ketone, aldehyde or nitrileis a compound having from 8 to 20 carbon atoms, or even more preferablybetween 10 and 15 carbon atoms.

According to a particular embodiment of the invention, said group Prorepresents a hydrogen atom or a group susceptible of generating anodoriferous α,β-unsaturated ketone, aldehyde or nitrile and isrepresented by the formulae

-   -   in which the wavy line indicates the location of the bond        between said Pro and the sulfur atom S;    -   R¹ represents a hydrogen atom, a C₁ to C₁₀ linear, cyclic or        branched alkyl, alkenyl or alkadienyl group, optionally        substituted by one to four C₁₋₃ alkyl groups; and    -   R² represents a hydrogen atom or a C₁₋₃ alkyl group or a phenyl        group optionally substituted by one or two C₁₋₃ alkyl groups;    -   R³ and R⁴ represent a hydrogen atom, a phenyl group, a C₇₋₉        phenylalkyl group or a C₁ to C₁₀ linear, cyclic or branched        alkyl, alkenyl or alkadienyl group, said R³ and R⁴ being        optionally substituted by one to four C₁₋₄ alkyl groups;    -   or two, or three, of the groups R¹ to R⁴ are bonded together to        form a saturated or unsaturated ring having 6 to 12 carbon atoms        and including the carbon atom to which said R¹, R², R³ or R⁴        groups are bonded, this ring being optionally substituted by one        to four C₁₋₄ linear, branched or cyclic alkyl or alkenyl groups;        and with the proviso that at least one of the Pro groups is of        the formula (II) or (II′) as defined hereinabove.

According to a particular embodiment of the invention, said group Prorepresents a hydrogen atom or a group of the formulae (P-1) to (P-16),in the form of any one of its isomers:

in which formulae the wavy line indicates the location of the bondbetween said Pro and the S atom, the dotted lines represent a single ordouble bond, R⁷ indicating a hydrogen atom or a methyl group; and withthe proviso that at least one of the Pro groups is of the formulae (P-1)to (P-16) as defined hereinabove.

According to any one of the invention's embodiments, said Pro group is agroup susceptible of generating an odoriferous α,β-unsaturated ketone,aldehyde, or nitrile, and in particular an odoriferous α,β-unsaturatedketone or aldehyde.

According to any one of the invention's embodiments, said group Prorepresents a hydrogen atom or a group susceptible of generating anodoriferous α,β-unsaturated ketone or aldehyde and is represented by theformula (II) as defined above.

According to any one of the invention's embodiments, said group Pro is agroup of the formulae (P-1) to (P-11), as defined above.

According to any one of the invention's embodiments, said group Pro is agroup of the formulae (P-1) to (P-7), as defined above.

According to any one of the invention's embodiments, said group Pro is agroup susceptible of generating an odoriferous compound selectedamongst: alpha-damascone, beta-damascone, gamma-damascone,delta-damascone, alpha-ionone, beta-ionone, gamma-ionone, delta-ionone,beta-damascenone, 3-methyl-5-propyl-2-cyclohexen-1-one, 1-(5,5- or3,3-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one,2-methyl-5-(prop-1-en-2-yl)cyclohex-2-enone (carvone), 8- or10-methyl-alpha-ionone, 2-octenal,1-(2,2,3,6-tetramethyl-1-cyclohexyl)-2-buten-1-one,4-(2,2,3,6-tetramethyl-1-cyclohexyl)-3-buten-2-one,2-cyclopentadecen-1-one, nootkatone, cinnamic aldehyde,2,6,6-trimethylbicyclo[3.1.1]heptane-3-spiro-2′-cyclohexen-4′-one and3,7-dimethylocta-2,6-dienal (citral).

Amongst the odoriferous compounds cited in the list hereinabove, it willbe preferably selected: the damascones, ionones, beta-damascenone,1-(5,5- or 3,3-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one, carvone,1-(2,2,3,6-tetramethyl-1-cyclohexyl)-2-buten-1-one,4-(2,2,3,6-tetramethyl-1-cyclohexyl)-3-buten-2-one and citral.

According to any one of the above embodiments of the invention, saidgroup X is an oxygen atom or an NR⁵ or NH group wherein R⁵ is a C₁₋₆alkyl group.

According to any one of the above embodiments of the invention, saidgroup X is an oxygen atom or an NH group, in particular an oxygen atom.

According to any one of the above embodiments of the invention, saidgroup R represents a linear or branched C₁-C₃, alkanediyl groupoptionally comprising a carboxylic acid or an alkaline carboxylategroup. Specific, and non-limiting, examples of said R is a CH(Me), CH₂,CH₂CH₂, CH₂CH₂CH₂, CH₂(CH₂)₂CH₂, CH(Me)CH₂ or a CH(CH₂COOH) orCH(CH₂COOM) group, M being an alkaline metal cation.

According to any one of the above embodiments of the invention, said mis an integer from 1 to 4, in particular it represents 1 or 2. Accordingto any one of the above embodiments of the invention, said m is 1.

According to any one of the above embodiments of the invention, saidgroup G represents:

-   -   a hydrogen atom, a sodium or potassium cation, an ammonium        cation or a C₁₋₈ quaternary amine cation;    -   a group of formula Si(R⁶)_(4-m), in which m is an integer from 1        to 4 and R⁶ represents a C₁₋₈ hydrocarbon or alkoxyl group;    -   a C₁₋₁₀, or even a C₁₋₇, linear, branched or cyclic alkyl,        alkenyl or aromatic group optionally comprising from 1 or 2        ether, ester, quaternary amines or ketone functional groups (in        which case m is 1);    -   a C₂₋₁₀ linear, branched or cyclic alkanediyl or benzenediyl        group optionally comprising from 1 or 2 ether, ester, quaternary        amines or ketone functional groups (in which case m is 2);    -   a C₄₋₁₀ branched or cyclic alkane-tri/tetra-yl group optionally        comprising from 1 or 2 ether, ester, quaternary amines or ketone        functional groups (in which case m is 3 or 4); or    -   a (CH₂CH₂O)_(q)R′ group with R′ being a hydrogen atom or a        methyl group and with q being an integer varying between 3 and        12.

According to any one of the above embodiments of the invention, saidgroup G represents:

-   -   a hydrogen atom, a sodium or potassium cation, the ammonium        cation or a C₁₋₈ quaternary amine cation;    -   a group of formula Si(R⁶)₃, R⁶ represents a C₁₋₃ alkyl or        alkoxyl group;    -   a C₁₋₅, or even a C₁₋₄, linear or branched alkyl group        optionally comprising from 1 or 2 ether or quaternary amines        functional groups; or    -   a (CH₂CH₂O)_(q)R′ group with R′ being a hydrogen atom or a        methyl group and with q being an integer varying between 8 and        12.

According to any one of the above embodiments of the invention, saidgroup G represents:

-   -   a hydrogen atom, a sodium or potassium cation, the ammonium        cation or a C₁₋₈ quaternary amine cation; or    -   a C₁₋₅, or even a C₁₋₄, linear or branched alkyl group.

According to any one of the above embodiments of the invention, saidgroup G represents a hydrogen atom, a sodium or potassium cation, theammonium cation or a C₁₋₈ quaternary amine cation, a Si(Me)₃ group or amethyl or ethyl group.

According to any one of the above embodiments of the invention, saidmoiety G[X—CO—R—SH]_(m), in particular when m is 1, is a C₂₋₈ group, inparticular a C₂₋₅ or a C₂₋₄ group.

Specific, and non-limiting, examples of said G group are the onesderived from the herein below examples of the G[X—CO—R—SH]_(m),compounds, i.e. when it is mentioned 2-ethylhexyl 3-mercaptopropionate,the corresponding G group is a 2-ethylhexyl group and m is 1.

It is understood that by the expression “a linear, branched or cyclic .. . alkyl, alkenyl or aromatic group”, or the similar, it is meant thatsaid group can be in the form of, e.g., a linear alkyl group or can alsobe in the form of a mixture of said type of groups, e.g. a specificgroup may comprise a linear alkyl, a branched alkenyl, a (poly)cyclicalkyl and an aryl moiety, unless a specific limitation to only one typeis mentioned. Similarly, in all the above and below embodiments of theinvention, when a group is mentioned as being in the form of more thanone type of topology (e.g. linear, cyclic or branched) and/or containsan unsaturation (e.g. alkyl, aromatic or alkenyl) it is meant also agroup which may comprise moieties having any one of said topologies orunsaturations, as above explained. Similarly, in all the above and belowembodiments of the invention when a group is mentioned as being in theform of a ring, said ring can be in a simple ring or a bicycle, a spirocycle, and etc.

According to any one of the above embodiments, said compound (I) is acompound of formula

wherein Pro and G are as defined above, n is 1 or 2, and R⁸ represents ahydrogen atom or a methyl group or a CH₂COOH or a CH₂COOM group, with Mbeing defined as above.

When m in formula (I) is equal to 2, 3 or 4, then each of the variousPro may be identical or different, as well as each of the R.

The compounds of formula (I) may be synthesized from commerciallyavailable compounds by conventional methods. Generally speaking, theinvention's compounds are obtainable by the [1,4]-addition reactionbetween an odoriferous α,β-unsaturated ketone, aldehyde or nitrile offormula

wherein the configuration of the carbon-carbon double bond can be of theE or Z type and the symbols R¹, R², R³ and R⁴ have the meaning indicatedabove; and a compound of formula G[X—CO—R—SH]_(m), wherein all thesymbols have the meaning given in formula (I).

A particular example of this approach is illustrated in the followingscheme:

Specific examples or alternative approaches are described in theexamples herein below.

Although it is not possible to provide an exhaustive list of thecompounds of formula G[X—CO—R—SH]_(m) which may be used in the synthesisof the invention's compounds, one can cite as preferred examples thefollowing: thioglycolic acid, ammonium thioglycolate, 2-ethylhexylthioglycolate, methyl thioglycolate, ethyl thioglycolate,2,3-dihydroxypropyl 2-mercaptoacetate, (9H-fluoren-9-yl)methyl2-mercaptoacetate, trimethylolpropane tris(thioglycolate),pentaerythritol tetra(mercaptoacetate), 2-mercaptopropionic acid,ammonium 2-mercaptopropionate, methyl 2-mercaptopropionate, ethyl2-mercaptopropionate, 2,3-dihydroxypropyl 2-mercaptopropionate,1-hydroxyethyl 2-mercaptoacetate, 2-hydroxypropyl 2-mercaptoacetate,3-hydroxypropyl 2-mercaptoacetate, 3-hydroxybutyl 2-mercaptoacetate,4-hydroxybutyl 2-mercaptoacetate, 3-mercaptopropionic acid, methyl3-mercaptopropionate, 3-mercapto-N,N-dimethylpropanamide, 2-ethylhexyl3-mercaptopropionate, 3-methoxybutyl 3-mercaptopropionate, octadecyl3-mercaptopropionate, butyl 3-mercaptopropionate,3-mercapto-2-methylpropanoic acid, pentaerythritoltetra-(3-mercaptopropionate), trimethylolpropanetris-(3-mercaptopropionate), 2-mercaptosuccinic acid, 4-mercaptobutanoicacid, 2-hydroxyethyl 2-mercaptoacetate, 2-methoxyethyl2-mercaptoacetate, 3-methoxybutyl thioglycolate,2,5,8,11-tetraoxamidecan-13-yl 2-mercaptoacetate,2,5,8,11,14,17,20,23,26,29,32,35-dodecaoxaheptatriacontan-37-yl2-mercaptoacetate, ethane-1,2-diyl bis(2-mercapto acetate),1,4-butanediol bis(thioglycolate), and(ethane-1,2-diylbis(oxy))bis(ethane-2,1-diyl)bis(2-mercaptoacetate).

Particularly preferred compounds of formula G[X—CO—R—SH]_(m) are thefollowing: thioglycolic acid, ammonium thioglycolate, methylthioglycolate, 2-mercaptopropionic acid, ammonium 2-mercaptopropionate,methyl 2-mercaptopropionate, 3-mercaptopropionic acid, methyl3-mercaptopropionate, 3-mercapto-2-methylpropanoic acid and2-mercaptosuccinic acid.

It is understood that the α,β-unsaturated ketone, aldehyde or nitrile offormulae (III) or (IV) are the odoriferous compounds released by thecompound of formula (I) upon decomposition. An example of saiddecomposition reaction is illustrated in the following scheme:

The residues of the decomposition reaction may be themselves odorlesscompounds, have themselves an odor or release a perfuming alcohol GOH.According to a particular embodiment, said residues are odorlesscompounds. Similarly, the compound of formula (I) is preferablyodorless.

The decomposition reaction, which leads to the release of theodoriferous molecules, is believed to be influenced by pH changes, thepresence of oxygen or other oxidants, enzymes or heat, but may betriggered by other types of mechanisms or the combination of severalmechanisms.

As mentioned above, the invention concerns the use of a compound offormula (I) as perfuming ingredient. In other words, it concerns amethod to confer, enhance, improve or modify the odor properties of aperfuming composition or of a perfumed article, which method comprisesadding to said composition or article an effective amount of at least acompound of formula (I). By “use of a compound of formula (I)” it has tobe understood here also the use of any composition containing a compound(I) and which can be advantageously employed in perfumery industry.

Said compositions, which in fact can be advantageously employed asperfuming ingredients, are also an object of the present invention.

Therefore, another object of the present invention is a perfumingcomposition comprising:

-   i) as perfuming ingredient, at least one invention's compound as    defined above;-   ii) at least one ingredient selected from the group consisting of a    perfumery carrier and a perfumery base; and-   iii) optionally at least one perfumery adjuvant.

By “perfumery carrier” we mean here a material which is practicallyneutral from a perfumery point of view, i.e. that does not significantlyalter the organoleptic properties of perfuming ingredients. Said carriermay be a liquid or a solid.

As liquid carrier one may cite, as non-limiting examples, an emulsifyingsystem, i.e. a solvent and a surfactant system, or a solvent commonlyused in perfumery. A detailed description of the nature and type ofsolvents commonly used in perfumery cannot be exhaustive. However, onecan cite as non-limiting examples solvents such as dipropyleneglycol,diethyl phthalate, isopropyl myristate, benzyl benzoate,2-(2-ethoxyethoxy)-1-ethanol or ethyl citrate, which are the mostcommonly used. For the compositions which comprise both a perfumerycarrier and a perfumery base, other suitable perfumery carriers thanthose previously specified, can be also water (in which case asolubilizing amount of surfactants may be necessary), ethanol,water/ethanol mixtures, limonene or other terpenes, isoparaffins such asthose known under the trademark Isopar® (origin: Exxon Chemical) orglycol ethers and glycol ether esters such as those known under thetrademark Dowanol® (origin: Dow Chemical Company).

As solid carriers one may cite, as non-limiting examples, absorbing gumsor polymers, or yet encapsulating materials. Examples of such materialsmay comprise wall-forming and plasticizing materials, such as mono, di-or trisaccharides, natural or modified starches, hydrocolloids,cellulose derivatives, polyvinyl acetates, polyvinylalcohols, proteinsor pectins, or yet the materials cited in reference texts such as H.Scherz, Hydrokolloide: Stabilisatoren, Dickungs- and Geliermittel inLebensmitteln, Band 2 der Schriftenreihe Lebensmittelchemie,Lebensmittelqualität, Behr's Verlag GmbH & Co., Hamburg, 1996. Theencapsulation is a well known process to a person skilled in the art,and may be performed, for instance, using techniques such asspray-drying, agglomeration or yet extrusion; or consists of a coatingencapsulation, including coacervation and complex coacervationtechnique.

By “perfumery base” we mean here a composition comprising at least oneperfuming co-ingredient.

Said perfuming co-ingredient is not of formula (I). Moreover, by“perfuming co-ingredient” it is meant here a compound, which is used ina perfuming preparation or a composition to impart a hedonic effect. Inother words such a co-ingredient, to be considered as being a perfumingone, must be recognized by a person skilled in the art as being able toimpart or modify in a positive or pleasant way the odor of acomposition, and not just as having an odor.

The nature and type of the perfuming co-ingredients present in the basedo not warrant a more detailed description here, which in any case wouldnot be exhaustive, the skilled person being able to select them on thebasis of his general knowledge and according to intended use orapplication and the desired organoleptic effect. In general terms, theseperfuming co-ingredients belong to chemical classes as varied asalcohols, lactones, aldehydes, ketones, esters, ethers, acetates,nitriles, terpenoids, nitrogenous or sulphurous heterocyclic compoundsand essential oils, and said perfuming co-ingredients can be of naturalor synthetic origin. Many of these co-ingredients are in any case listedin reference texts such as the book by S. Arctander, Perfume and FlavorChemicals, 1969, Montclair, N.J., USA, or its more recent versions, orin other works of a similar nature, as well as in the abundant patentliterature in the field of perfumery. It is also understood that saidco-ingredients may also be compounds known to release in a controlledmanner various types of perfuming compounds, or can be an encapsulatedperfume.

By “perfumery adjuvant” we mean here an ingredient capable of impartingadditional added benefit such as a color, a particular light resistance,chemical stability, etc. A detailed description of the nature and typeof adjuvant commonly used in perfuming bases cannot be exhaustive, butit has to be mentioned that said ingredients are well known to a personskilled in the art.

An invention's composition consisting of at least one compound offormula (I) and at least one perfumery carrier represents a particularembodiment of the invention as well as a perfuming compositioncomprising at least one compound of formula (I), at least one perfumerycarrier, at least one perfumery base, and optionally at least oneperfumery adjuvant.

It is useful to mention here that the possibility to have, in thecompositions mentioned above, more than one compound of formula (I) isimportant as it enables the perfumer to prepare accords, perfumes,possessing the odor tonality of various compounds of the invention,creating thus new tools for his work.

Furthermore, the invention's compound can also be advantageously used inall the fields of modern perfumery, i.e. fine or functional perfumery,to positively impart or modify the odor of a consumer product into whichsaid compound (1) is added. Indeed, for example, the invention'scompounds are capable of levitating problems often encountered withclassical perfuming ingredients present as such which in washing orperfuming compositions can have little staying-power on a surface andconsequently are often eliminated, for example in the rinsing water orupon drying of surfaces such as textiles, hard surfaces, hair and skin.

Consequently, a perfuming consumer product which comprises:

-   -   i) as perfuming ingredient, at least one compound of formula        (I), as defined above; and    -   ii) a perfumery consumer base; is also an object of the present        invention.

The invention's compound can be added as such or as part of aninvention's perfuming composition.

For the sake of clarity, it has to be mentioned that, by “perfumingconsumer product” it is meant a consumer product which is expected todeliver at least a perfuming effect, in other words it is a perfumedconsumer product. For the sake of clarity, it has to be mentioned that,by “perfumery consumer base” we mean here the functional formulation, aswell as optionally additional benefit agents, corresponding to aconsumer product which is compatible with perfuming ingredients and isexpected to deliver a pleasant odor to the surface to which it isapplied (e.g. skin, hair, textile, or home surface). In other words, aperfuming consumer product according to the invention comprises thefunctional formulation, as well as optionally additional benefit agents,corresponding to the desired consumer product, e.g. a detergent or anair freshener, and an olfactive effective amount of at least oneinvention's compound.

The nature and type of the constituents of the perfumery consumer basedo not warrant a more detailed description here, which in any case wouldnot be exhaustive, the skilled person being able to select them on thebasis of his general knowledge and according to the nature and thedesired effect of said product.

Non-limiting examples of suitable perfumery consumer base can be aperfume, such as a fine perfume, a cologne or an after-shave lotion; afabric care product, such as a liquid or solid detergent, a fabricsoftener, a fabric refresher, an ironing water, a paper, or a bleach; abody-care product, such as a hair care product (e.g. a shampoo, acoloring preparation or a hair spray), a cosmetic preparation (e.g. avanishing cream or a deodorant or antiperspirant), or a skin-careproduct (e.g. a perfumed soap, shower or bath mousse, oil or gel, or ahygiene product); an air care product, such as an air freshener or a“ready to use” powdered air freshener; or a home care product, such as awipe, a dish detergent or hard-surface detergent.

Preferred perfuming compositions or perfumed articles are perfumes,fabric or hard-surface detergents, hair care product or softener bases.

Typical examples of fabric detergents or softener compositions intowhich the compounds of the invention can be incorporated are describedin WO 97/34986, in WO 2012/113756 or in U.S. Pat. Nos. 4,137,180 and5,236,615 or in EP 799 885. Other typical detergents and softeningcompositions which can be used are described in works such as Ullman'sEncyclopedia of Industrial Chemistry, vol. A8, pages 315-448 (1987) andvol. A25, pages 747-817 (1994); Flick, Advanced Cleaning ProductFormulations, Noye Publication, Park Ridge, N.J. (1989); Showell, inSurfactant Science Series, vol. 71: Powdered Detergents, Marcel Dekker,New York (1988); Proceedings of the World Conference on Detergents (4th,1998, Montreux, Switzerland), AOCS print.

Some of the above-mentioned consumer product bases may represent anaggressive medium for the invention's compound, so that it may benecessary to protect the latter from premature decomposition, forexample by encapsulation or by chemically bounding it to anotherchemical which is suitable to release the invention's ingredient upon asuitable external stimulus, such as an enzyme, light, heat or a changeof pH.

The proportions in which the compounds according to the invention can beincorporated into the various aforementioned articles or compositionsvary within a wide range of values. These values are dependent on thenature of the article to be perfumed and on the desired organolepticeffect as well as the nature of the co-ingredients in a given base whenthe compounds according to the invention are mixed with perfumingco-ingredients, solvents or additives commonly used in the art.

For example, in the case of perfuming compositions, typicalconcentrations are in the order of 0.001% to 5% by weight, or even more,of the compounds of the invention based on the weight of the compositioninto which they are incorporated. Concentrations lower than these, suchas in the order of 0.01% to 1% by weight, can be used when thesecompounds are incorporated into perfumed articles, percentage beingrelative to the weight of the article.

EXAMPLES

The invention will now be described in further detail by way of thefollowing examples, wherein the abbreviations have the usual meaning inthe art, the temperatures are indicated in degrees centigrade (° C.);the NMR spectral data were recorded in CDCl₃ (if not stated otherwise)with a 360 or 400 MHz machine for ¹H and ¹³C, the chemical displacementδ are indicated in ppm with respect to the TMS as standard, the couplingconstants J are expressed in Hz.

Example 1 Synthesis of Compounds of Formula (I) i) Synthesis of2-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)aceticacid

(E)-1-((1RS,2SR)-2,6,6-trimethylcyclohex-3-enyl)but-2-en-1-one(delta-damascone; 47.0 g, 244 mmol) and 2-mercaptoacetic acid (22.0 g,239 mmol) were stirred for 23 h at room temperature. The reactionmixture was diluted with methyl tert-butyl ether (MTBE; 35 ml), washedseveral times with H₂O and concentrated under vacuum at a maximumtemperature of 50° C. The crude title compound (60.0 g; ca. 1:1diastereoisomeric mixture), containing some residual delta-damascone,can be used as such. A sample was further purified by flashchromatography on silica gel using a mixture of MTBE and n-heptane (10%up to 50% in MTBE) as the eluent.

¹³C-NMR: 19.9 (q), 20.7 (q), 21.1/21.3 (q), 29.7 (q), 31.6/31.8 (d),32.9/33.1 (t), 33.1/33.2 (s), 35.6 (d), 41.7 (t), 54.6/54.8 (t),62.8/62.9 (d), 124.1/124.3 (d), 131.7/131.8 (d), 176.4/176.5 (s),212.2/212.3 (s).

¹H-NMR: 0.87-0.92 (m, 3H); 0.94-1.01 (m, 6H); 1.32-1.37 (m, 3H);1.66-1.74 (m, 1H); 1.92-2.01 (m, 1H); 2.19-2.25 (m, 1H); 2.46-2.62 (m,1.5H); 2.75-2.79 (2s, 1H); 2.93-3.01 (m, 0.5H); 3.33-3.49 (m, 3H);5.42-5.48 (m, 1H); 5.50-5.58 (m, 1H); 11.25 (s, 1H).

ii) Synthesis of2-((3-oxo-1-(2,6,6-trimethylcyclohex-2-en-1-yl)pentyl)thio)acetic acid

(E)-1-(2,6,6-trimethylcyclohex-2-enyl)pent-1-en-3-one (main isomer of anisomeric mixture; 10.0 g, 48.5 mmol) and ammonium thioglycolate (70%aqueous solution; 8.4 g, 53.9 mmol) were stirred at room temperature for9 d. The reaction mixture was diluted with water (30 ml), then extractedwith MTBE (30 ml) in order to remove unreacted substrate. The aqueousphase containing the ammonium carboxylates was acidified with aqueousHCl (10%) and extracted with MTBE (2×50 ml). The combined organic phaseswere washed with H₂O and brine, dried over anhydrous Na₂SO₄, filteredand concentrated under vacuum (0.1 mbar) at a maximum temperature of 70°C. The crude target compound (5.1 g, viscous oil) can be used as such.

¹³C-NMR: 7.7 (q), 22.8/23.1 (t), 25.2 (q), 27.5 (q), 28.5/28.7 (q),31.1/31.7 (t), 33.4/33.5 (s), 34.6/35.5 (t), 36.6/36.7 (t), 40.0/41.9(d), 47.6/50.1 (t), 54.2/55.1 (d), 123.7/124.9 (d), 132.0/133.3 (s),176.1/176.6 (s), 210.1 (s).

¹H-NMR: 0.84-1.12 (m, 9H); 1.12-1.66 (m, 2H); 1.75-2.09 (m, 6H);2.38-2.54 (m, 2H); 2.59-3.00 (m, 2H); 3.20-3.50 (m, 2H); 3.70-3.85 (m,1H); 5.45-5.53 (m, 1H); 10.54 (s, 1H).

iii) Synthesis of 2-((2-formyl-1-phenyloctyl)thio)acetic acid

Using the same experimental procedure as described in Example ii, thetitle compound was obtained from hexylcinnamic aldehyde and ammoniumthioglycolate. The crude title compound (28.9 g; pale yellow liquid; 2:1diastereoisomeric mixture), containing some residual hexylcinnamicaldehyde, can be used as such. A sample was further purified by flashchromatography on silica gel using a mixture of MTBE and n-heptane (3%up to 80% in MTBE) as the eluent.

¹³C-NMR: 14.0 (q), 22.4 (t), 26.5 (t), 28.5 (t), 28.9 (t), 31.4 (t),31.7 (t), 49.3 (d), 56.3 (d), 128.1 (d), 128.7 (2d), 128.8 (2d), 138.3(s), 175.4 (s), 202.1 (d).

¹H-NMR: 0.77-0.90 (m, 3H); 1.05-1.86 (m, 11H); 2.86-2.97 (m, 1H);2.97-3.10 (m, 1H); 3.57-3.64 (m, 1H); 4.20-4.39 (m, 1H); 7.22-7.38 (m,5H); 9.48-9.65 (m, 1H).

iv) Synthesis of ammonium2-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)acetate

Delta-damascone (18.5 g, 96 mmol) and ammonium thioglycolate (70%aqueous solution; 16.5 g, 106 mmol) were stirred at room temperature for42 h. The reaction mixture was diluted with water (50 ml), and thenextracted with MTBE (2×30 ml). Remaining starting material (3.2 g) wasrecovered from the combined organic phases by removing the solvent underreduced pressure. The aqueous phase containing the target ammoniumcarboxylate was concentrated under vacuum yielding the target compound(28.0 g; ca. 1:1 diastereoisomeric mixture) as a white semi-crystallinematerial (97% yield).

¹³C-NMR: 19.3/19.4 (q), 20.5 (q), 20.7/21.0 (q), 29.1 (q), 30.9/31.2(d), 32.4/32.5 (s), 33.7 (d), 35.6/35.7 (t), 40.9 (t), 54.1 (t),61.2/61.4 (d), 124.0/124.1 (d), 131.5 (d), 172.4 (s), 212.1/212.2 (s).

¹H-NMR: 0.81-0.87 (m, 6H); 0.92-0.97 (m, 3H); 1.16-1.22 (m, 3H);1.61-1.70 (m, 1H); 1.91-2.01 (m, 1H); 2.24-2.41 (m, 2H); 2.49-2.54 (m,1H); 2.70-2.78 (m, 1H); 3.04-3.09 (m, 2H); 3.20-3.29 (m, 1H); 5.41-5.47(m, 1H); 5.50-5.56 (m, 1H); 6.80 (broad, NH₄).

v) Synthesis of trimethylsilyl2-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)acetate

2-((4-Oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)aceticacid (Example i; 3.0 g, 10.6 mmol) and2,2,2-trifluoro-N-methyl-N-(trimethylsilyl)acetamide (MSTFA; 3.0 ml)were heated at 40° C. for 4 h. The reaction mixture was purified byvacuum distillation (bulb to bulb distillation, 120° C., 0.1 mbar),affording 1.5 g of the title compound.

¹³C-NMR: −0.33 (q), 19.9 (q), 20.7 (q), 21.2/21.4 (q), 29.8 (q),31.6/31.8 (d), 33.1/33.2 (s), 34.7/34.8 (t), 35.3 (d), 41.7 (t),54.8/54.9 (t), 62.8/62.9 (d), 124.1/124.3 (d), 131.7/131.8 (d), 170.8(s), 212.0/212.1 (s).

¹H-NMR: 0.29-0.33 (m, 9H); 0.86-0.92 (m, 3H); 0.93-1.01 (m, 6H);1.30-1.37 (m, 3H); 1.65-1.74 (m, 1H); 1.92-2.01 (m, 1H); 2.18-2.26 (m,1H); 2.46-2.63 (m, 1.5H); 2.72-2.79 (m, 1H); 2.91-3.02 (m, 0.5H);3.27-3.47 (m, 3H); 5.41-5.48 (m, 1H); 5.50-5.58 (m, 1H).

vi) Synthesis of methyl2-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)acetate

Delta-damascone (36.0 g, 187 mmol) and methyl 2-mercaptoacetate (15.0 g,141 mmol) were stirred for 15 d at room temperature, yielding a mixtureof the target compound and delta-damascone. Removal of volatileimpurities at 40° C. under high vacuum gave 47.5 g (93% weight yield) ofa mixture which can be used as such. A pure sample (99%; twodiastereoisomers ca. 1:1) was obtained by flash-chromatography(heptane/MTBE 95:5) on SiO₂.

¹³C-NMR: 19.9 (q), 20.7 (q), 21.1/21.3 (q), 29.8 (q), 31.6/31.8 (d),32.8/32.9 (t), 33.1/33.2 (s), 35.4 (d), 41.7 (t), 52.4 (t), 54.7/54.8(t), 62.8/62.9 (d), 124.1/124.3 (d), 131.7/131.8 (d), 171.0 (s),211.9/212.0 (s).

¹H-NMR: 0.87-0.92 (m, 3H); 0.94-1.01 (m, 6H); 1.32-1.37 (m, 3H);1.66-1.74 (m, 1H); 1.93-2.01 (m, 1H); 2.19-2.25 (m, 1H); 2.46-2.60 (m,2H); 2.73-2.77 (m, 1H); 3.29-3.47 (m, 3H); 3.739-3.743 (2s, 3H);5.42-5.48 (m, 1H); 5.50-5.58 (m, 1H).

vii) Synthesis of methyl2-((3-oxo-1-(2,6,6-trimethylcyclohex-2-en-1-yl)butyl)thio)acetate

This compound was prepared by stirring(E)-4-(2,6,6-trimethylcyclohex-2-en-1-yl)but-3-en-2-one (alpha-ionone;5.0 g, 26.0 mmol), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU; 0.25 g) andan excess of methyl 2-mercaptoacetate (10.0 g) at room temperature.After 11 h, the reaction was quenched with aqueous citric acid. Thereaction mixture was diluted with MTBE (15 ml), washed several timeswith H₂O, then with brine, dried over anhydrous Na₂SO₄, filtered andconcentrated under vacuum at a maximum temperature of 50° C. The crudetitle compound (16.0 g), containing some residual alpha-ionone, can beused as such. A sample was further purified by flash-chromatography(heptane/MTBE 70:30) on SiO₂.

¹³C-NMR: 22.9/23.1 (t), 25.3/25.9 (q), 27.3/27.4 (q), 28.6/29.1 (q),30.6 (q), 31.7 (t), 33.3/33.5 (s), 35.3 (t), 39.6 (d), 48.5/48.7 (t),52.4/52.6 (q), 54.7/55.0 (d), 123.1/123.7 (d), 133.4/133.8 (s),171.0/171.3 (s), 206.7 (s).

¹H-NMR: 0.87 (s, 0.7H); 0.92 (s, 2.3H); 1.02 (s, 3H); 1.10-1.33 (m, 2H);1.46 (s, 1H); 1.78-1.88 (m, 3H); 1.94-2.05 (m, 3H); 2.15 (s, 2H);2.67-2.75 (m, 1H); 3.25-3.39 (m, 2H); 3.73-3.82 (m, 5H); 5.40-5.50 (m,1H).

viii) Synthesis of (E)-methyl2-((1-cyano-2,6-dimethyloct-5-en-2-yl)thio)acetate-(Z)-methyl2-((1-cyano-2,6-dimethyloct-5-en-2-yl)thio)acetate mixture

Using the same experimental procedure as described in Example vii thetitle compound was obtained from 3,7-dimethylnona-2,6-dienenitrile(Lemonile®; origin: Givaudan SA) and methyl 2-mercaptoacetate. The crudetarget compound (isomeric mixture (Z/E) 40:60; still containing someresidual Lemonile®) can be used as such. Purification by vacuumdistillation (bulb to bulb distillation, 135-140° C., 0.1 mbar)afforded >99% pure title compound mixture.

¹³C-NMR (deduced from the mixture): major isomer (E), 55% of themixture, 12.7 (q), 16.0 (q), 22.9 (t), 25.5 (q), 30.6 (t), 30.9 (t),32.3 (t), 39.6 (t), 46.9 (s), 52.7 (q), 116.9 (s), 121.2 (d), 138.3 (s),170.9 (s); minor isomer (Z), 45% of the mixture, 12.8 (q), 16.0 (q),22.6 (t), 24.8 (t), 25.5 (q), 30.6 (2t), 39.9 (t), 46.9 (s), 52.7 (q),116.9 (s), 122.3 (d), 138.6 (s), 170.9 (s).

¹H-NMR: 0.95-1.01 (m, 3H); 1.43-1.46 (m, 3H); 1.61-1.63 (m, 2H);1.66-1.74 (m, 3H); 1.94-2.19 (m, 4H); 2.69-2.73 (m, 2H); 3.28-3.32 (m,2H); 3.75 (s, 3H); 5.01-5.12 (m, 1H).

ix) Synthesis of 2,3-dihydroxypropyl2-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)acetate

This compound was prepared by stirring delta-damascone (15.0 g, 78mmol)), DBU (0.3 g) and a slight excess glycerol monothioglycolate (17.5g) at room temperature. After 2.5 h the reaction was quenched withaqueous citric acid. The reaction mixture was diluted with methylenechloride (15 ml), washed several times with H₂O then brine, dried overanhydrous Na₂SO₄, filtered and concentrated under high vacuum at amaximum temperature of 50° C. The crude title compound (21.9 g; mixtureof diastereoisomers; 78% yield) can be used as such.

¹³C-NMR: 19.9 (q), 20.7 (q), 21.2/21.3 (q), 29.7/29.8 (q), 31.6/31.7(d), 32.8/32.9 (t), 33.2 (s), 34.9/35.0 (d), 41.6/41.7 (t), 54.6/54.7(t), 63.0 (d), 63.2/63.3 (t), 66.2/66.3 (t), 69.9/70.0 (d), 124.1/124.3(d), 131.6/131.8 (d), 170.7 (s), 211.8/211.9 (s).

¹H-NMR: 0.85-1.04 (m, 9H); 1.28-1.37 (m, 3H); 1.65-1.75 (m, 1H);1.83-2.13 (m, 2H); 2.19-2.25 (m, 1H); 2.46-2.62 (m, 1.5H); 2.73-2.77 (m,1H); 2.89-2.98 (m, 0.5H); 3.26-3.54 (m, 4H); 3.60-3.69 (m, 1H);3.70-4.048 (m, 2H); 4.16-4.33 (m, 2H); 5.42-5.48 (m, 1H); 5.50-5.58 (m,1H).

x) Synthesis of 3-methoxybutyl2-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)acetate

Delta-damascone (14.0 g, 72.8 mmol), DBU (0.25 g) and 3-methoxybutyl2-mercaptoacetate (12.0 g, 67.3 mmol) were stirred at room temperature.After 3 h the reaction was quenched with aqueous citric acid. Thereaction mixture was diluted with MTBE (10 ml), washed several timeswith H₂O, then with brine, dried over anhydrous Na₂SO₄, filtered andconcentrated under high vacuum at a maximum temperature of 50° C. Thecrude title compound (24.1 g; mixture of diastereoisomers) can be usedas such. Further purification by vacuum distillation (bulb to bulbdistillation, 170-200° C., 0.1 mbar) afforded 15.0 g (60% yield) of puretitle compound.

¹³C-NMR: 19.1 (q), 19.9 (q), 20.7 (q), 21.1/21.3 (q), 29.8 (q),31.6/31.8 (d), 33.0/33.1 (t), 33.1/33.2 (s), 35.3 (d), 35.5 (t), 41.7(t), 54.7/54.8 (t), 56.1 (q), 62.4 (t), 62.8/62.9 (d), 73.5 (d),124.1/124.3 (d), 131.7/131.8 (d), 170.5 (s), 211.8/211.9 (s).

¹H-NMR: 0.87-0.92 (m, 3H); 0.94-1.01 (m, 6H); 1.15-1.20 (m, 3H),1.30-1.35 (m, 3H); 1.66-1.74 (m, 1H); 1.74-1.87 (m, 2H), 1.93-2.01 (m,1H); 2.19-2.25 (m, 1H); 2.46-2.60 (m, 2H); 2.73-2.77 (m, 1H); 3.27-3.35(m, 5H); 3.39-348 (m, 2H), 4.20-4.27 (m, 2H), 5.42-5.48 (m, 1H);5.50-5.58 (m, 1H).

xi) Synthesis of 2-ethylhexyl2-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)acetate

Delta-damascone (14.12 g, 73.4 mmol) and 2-ethylhexyl 2-mercaptoacetate(10.0 g, 48.9 mmol) were stirred at room temperature for 72 h. Theresulting mixture, containing the title compound and some residualdelta-damascone, can be used as such. A sample of the pure targetcompound was obtained by bulb to bulb distillation (180° C., 0.1 mbar).

¹³C-NMR: 11.0 (q), 14.0 (q), 19.9 (q), 20.7 (q), 21.1/21.3 (q), 23.0(t), 23.7 (t), 28.9 (t), 29.8 (q), 30.3 (t), 31.6/31.8 (d), 33.0/33.1(t), 33.1/33.3 (s), 35.3 (d), 38.7 (d), 41.7 (t), 54.7/54.8 (t),62.8/62.9 (d), 67.8 (t), 124.1/124.3 (d), 131.7/131.8 (d), 170.8 (s),211.8/211.9 (s).

¹H-NMR: 0.87-0.92 (m, 9H); 0.94-1.01 (m, 6H); 1.26-1.42 (m, 11H);1.55-1.74 (m, 2H); 1.92-2.01 (m, 1H); 2.18-2.24 (m, 1H); 2.52 (m, 1H);2.56, 2.96 (m, 1H); 2.73-2.77 (2s, 1H); 3.27-3.32 (m, 2H); 3.38-3.48 (m,1H); 4.01-4.10 (m, 2H); 5.41-5.48 (m, 1H); 5.50-5.58 (m, 1H).

xii) Synthesis of 2-ethylhexyl2-((3-oxo-1-(2,6,6-trimethylcyclohex-2-en-1-yl)pentyl)thio)acetate

This compound was prepared by stirring(E)-1-(2,6,6-trimethylcyclohex-2-enyl)pent-1-en-3-one (main isomer of anisomeric mixture; 10.0 g, 48.5 mmol), DBU (1.0 g) and 2-ethylhexyl2-mercaptoacetate (15.0 g, 73.4 mmol) at room temperature. After 1 h thereaction was quenched with aqueous citric acid. The reaction mixture wasdiluted with MTBE (10 ml), washed with H₂O and brine, dried overanhydrous Na₂SO₄, filtered and concentrated under high vacuum (0.1 mbar)at a maximum temperature of 140° C. The crude title compound (16.0 g;mixture of diastereoisomers, ratio 44:26:26:3 by NMR) can be used assuch.

¹³C-NMR (major isomer): 7.7 (q), 11.0 (q), 14.0 (q), 22.9 (t), 23.0 (t),23.7 (t), 25.3 (q), 27.6 (q), 28.6 (q), 28.9 (t), 30.3 (t), 31.7 (t),33.5 (s), 35.7 (t), 36.6 (t), 38.7 (d), 40.0 (d), 47.5 (t), 55.0 (d),67.8 (t), 123.6 (d), 133.6 (s), 170.8 (s), 209.4 (s).

¹H-NMR (major isomer): 0.85-1.00 (m, 11H); 1.00-1.19 (m, 6H); 1.23-1.43(m, 10H); 1.53-1.76 (m, 2H); 1.77-1.90 (m, 4H); 1.90-2.07 (m, 3H);2.36-3.91 (m, 3H); 3.96-4.14 (m, 2H); 5.38-5.52 (m, 1H).

xiii) Synthesis of (9H-fluoren-9-yl)methyl2-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)acetate

Methyl2-(4-oxo-4-((1S,2R)-2,6,6-trimethylcyclohex-3-enyl)butan-2-ylthio)acetate(Example vi; 24.0 g, 52.3 mmol), dioctylstannanone (0.6 g),9-fluorenylmethanol (10.0 g, 51.0 mmol) and n-heptane (50 ml) wererefluxed for 4 h with azeotropic removal of methanol. The solvent aswell as some of the remaining starting material was removed under highvacuum (0.1 mbar, 120° C.). Flash-chromatography (heptane/MTBE 95:5) onSiO₂ yielded the target compound (12.7 g, 53% yield).

¹³C-NMR: 19.9 (q), 20.7 (q), 21.2/21.3 (q), 29.8 (q), 31.6/31.8 (d),33.1 (s), 33.1/33.2 (t), 35.4 (d), 41.7 (t), 46.7 (d), 54.7/54.8 (t),62.7/62.8 (d), 67.3 (t), 120.0 (d), 124.1/124.2 (d), 125.1 (d), 127.1(d), 127.8 (d), 131.7/131.8 (d), 141.3 (s), 143.6 (s), 170.4 (s),211.8/211.9 (s).

¹H-NMR: 0.85-0.90 (m, 3H); 0.91-0.98 (m, 6H); 1.28-1.34 (m, 3H);1.63-1.72 (m, 1H); 1.90-1.99 (m, 1H); 2.16-2.22 (m, 1H); 2.46-2.59 (m,1.5H); 2.73-2.77 (m, 1H); 2.91-2.99 (m, 0.5H); 3.34-3.47 (m, 3H);4.20-4.27 (m, 1H); 4.41-4.44 (m, 2H); 5.40-5.47 (m, 1H); 5.50-5.57 (m,1H); 7.28-7.35 (m, 2H); 7.36-7.43 (m, 2H); 7.62-7.77 (m, 2H); 7.74-7.78(m, 2H).

xiv) Synthesis of 4-(2-mercaptoacetoxy)butyl2-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)acetate

Delta-damascone (8.0 g, 41.6 mmol) and butane-1,4-diylbis(2-mercaptoacetate) (8.0 g, 33.6 mmol) were stirred for 16 h at roomtemperature yielding a mixture of the target compound, delta-damasconeand(S,R)-butane-1,4-diylbis(2-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)acetate).This mixture (16.0 g) can be used as such. A pure sample (96%; twodiastereoisomers ca. 1:1) was obtained by flash-chromatography(heptane/MTBE 60:40) on SiO₂.

¹³C-NMR: 19.9 (q), 20.8 (q), 21.2/21.4 (q), 25.1 (t), 25.2 (t), 26.5(t), 29.8 (q), 31.6/31.8 (d), 33.0/33.1 (t), 33.1/33.2 (s), 35.3 (d),41.7 (t), 54.7/54.8 (t), 62.8/62.9 (d), 64.7 (t), 65.1 (t), 124.1/124.3(d), 131.7/131.8 (d), 170.5/170.6 (s), 170.8 (s), 211.9/212.0 (s).

¹H-NMR: 0.87-0.92 (m, 3H); 0.93-1.01 (m, 6H); 1.30-1.35 (m, 3H);1.72-1.79 (m, 5H); 1.92-2.04 (m, 2H); 2.18-2.24 (m, 1H); 2.45-2.59 (m,1.5H); 2.72-2.76 (m, 1H); 2.91-2.99 (m, 0.5H); 3.23-3.32 (m, 4H);3.39-3.47 (m, 1H); 4.14-4.21 (m, 4H); 5.42-5.48 (m, 1H); 5.50-5.58 (m,1H).

xv) Synthesis of (S,R)-butane-1,4-diylbis(2-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)acetate)

Using the same experimental procedure as described in Example xiv, butallowing a longer reaction time (66 h) gave a mixture (14 g) containingthe title compound as the major ingredient. A pure sample (98%; twodiastereoisomers ca. 1:1) was obtained by flash-chromatography(heptane/MTBE 70:30) on SiO₂.

¹³C-NMR: 19.9 (q), 20.7 (q), 21.2/21.4 (q), 25.2 (t), 29.8 (q),31.6/31.8 (d), 33.1/33.2 (s), 33.0/33.1 (t), 35.3 (d), 41.7 (t),54.7/54.8 (t), 62.8/62.9 (d), 64.8 (t), 124.1/124.3 (d), 131.7/131.8(d), 170.5 (s), 211.8/211.9 (s).

¹H-NMR: 0.87-0.92 (m, 6H); 0.93-1.01 (m, 12H); 1.30-1.35 (m, 6H);1.66-1.78 (m, 6H); 1.92-2.01 (m, 2H); 2.18-2.24 (m, 2H); 2.46-2.59 (m,3H); 2.73-2.77 (m, 2H); 2.91-2.99 (m, 1H); 3.27-3.33 (m, 4H); 3.39-3.47(m, 2H); 4.14-4.21 (m, 4H); 5.42-5.48 (m, 2H); 5.50-5.58 (m, 2H).

xvi) Synthesis of(S,R)-2-ethyl-2-((2-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)acetoxy)methyl)propane-1,3-diylbis(2-((4-oxo-4-((1S,2R)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)acetate)

Delta-damascone (33.0 g, 172 mmol) and2-ethyl-2-((2-mercaptoacetoxy)methyl)propane-1,3-diylbis(2-mercaptoacetate) (10.5 g, 29.5 mmol) were stirred for 12 d at roomtemperature yielding a mixture of delta-damascone, the target compound,(S,R)-2-ethyl-2-((2-mercaptoacetoxy)methyl)propane-1,3-diylbis(2-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)acetate)and2-ethyl-2-((2-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)acetoxy)methyl)propane-1,3-diylbis(2-mercaptoacetate). Removal of traces of volatile impurities underhigh vacuum at 50° C. gave a mixture (42.0 g) that can be used as such.A pure sample (90%) of the title compound was obtained byflash-chromatography (heptane/MTBE 70:30) on SiO₂.

¹³C-NMR: 7.38 (q), 19.9 (q), 20.7 (q), 21.2/21.4 (q), 29.8 (q),31.6/31.8 (d), 32.9/33.0 (t), 33.1/33.2 (s), 35.4 (d), 41.1 (s), 41.7(t), 54.7/54.8 (t), 62.8/62.9 (d), 64.5 (t), 124.1/124.3 (d),131.7/131.8 (d), 170.1 (s), 211.7/211.8 (s).

¹H-NMR: 0.86-0.92 (m, 12H); 0.93-1.00 (m, 18H); 1.29-1.34 (m, 9H);1.50-1.57 (m, 2H), 1.66-1.74 (m, 3H); 1.93-2.01 (m, 3H); 2.18-2.24 (m,3H); 2.47-2.97 (m, 9H); 3.30-3.34 (m, 6H); 3.36-3.46 (m, 3H); 4.12 (s,6H); 5.42-5.48 (m, 3H); 5.50-5.57 (m, 3H).

xvii) Synthesis of2-((2-mercaptoacetoxy)methyl)-2-((2-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)acetoxy)methyl)propane-1,3-diylbis(2-mercaptoacetate)

Delta-damascone (27.0 g, 140 mmol) and pentaerythritoltetrakis(2-mercaptoacetate) (10.0 g, 23.1 mmol) were stirred for 14 d atroom temperature yielding a mixture of delta-damascone, the targetcompound,(S,R)-2-((2-mercaptoacetoxy)methyl)-2-((2-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)acetoxy)methyl)propane-1,3-diylbis(2-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)acetate),2,2-bis((2-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)acetoxy)methyl)propane-1,3-diylbis(2-mercaptoacetate) and2-((2-mercaptoacetoxy)methyl)-2-((2-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)acetoxy)methyl)propane-1,3-diylbis(2-mercaptoacetate). Removal of traces of volatile impurities underhigh vacuum at 50° C. gave a mixture (36.3 g) that can be used as such.A pure sample (90%) of the title compound was obtained byflash-chromatography (heptane/MTBE 70:30) on SiO₂.

¹³C-NMR: 19.9 (q), 20.7 (q), 21.2/21.4 (q), 29.8 (q), 31.6/31.8 (d),32.8/32.9 (t), 33.1/33.2 (s), 35.5 (d), 41.7 (t), 42.5 (s), 54.6/54.8(t), 62.8/62.9 (d), 62.9 (t), 124.1/124.3 (d), 131.7/131.8 (d), 169.9(s), 211.7/211.8 (s).

¹H-NMR: 0.87-0.92 (m, 12H); 0.93-1.00 (m, 24H); 1.31-1.33 (m, 12H);1.66-1.74 (m, 4H); 1.93-2.01 (m, 4H); 2.18-2.24 (m, 4H); 2.47-2.97 (m,12H); 3.31-3.44 (m, 12H); 4.25 (s, 8H); 5.42-5.48 (m, 4H); 5.51-5.58 (m,4H).

xviii) Synthesis of(S,R)-2-(2-mercaptoacetoxy)methyl)-2-((2-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)acetoxy)methyl)propane-1,3-diylbis(2-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)acetate)

Using the same experimental procedure as described in Example xvii, butallowing a shorter reaction time (8 d), yielded a mixture containing thetarget compound. A pure sample (ca. 80%) was obtained byflash-chromatography (heptane/MTBE 70:30) on SiO₂.

¹³C-NMR: 19.9 (q), 20.7 (q), 21.2/21.4 (q), 29.8 (q), 31.6/31.8 (d),32.8/32.9 (t), 33.1/33.2 (s), 35.4 (d), 41.7 (t), 42.5/42.6 (s),54.6/54.7 (t), 62.8/62.9 (d), 62.9 (t), 124.1/124.3 (d), 131.7/131.8(d), 169.9 (s), 211.7/211.8 (s).

¹H-NMR: 0.87-0.92 (m, 9H); 0.93-1.00 (m, 18H); 1.31-1.33 (m, 9H);1.66-1.74 (m, 3H); 1.88-2.01 (m, 4H); 2.19-2.25 (m, 3H); 2.47-2.97 (m,9H); 3.28-3.44 (m, 11H); 4.21-4.25 (m, 8H); 5.42-5.48 (m, 3H); 5.51-5.58(m, 3H).

xix) Synthesis of 2-methoxyethyl2-((4-oxo-4-(2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)acetate

2-Methoxyethanol (3.66 g, 48.1 mmol), thioglycolic acid (5.00 ml, 72.2mmol) and dry toluene (50 ml) were stirred and a catalytic amount ofsulfuric acid (one drop) was added. The solution was refluxed overnight.After cooling to room temperature, the solvent was evaporated to give acolorless oil. The oil was taken up in dichloromethane (50 ml) andwashed with water (2 twice 20 ml) and brine (40 ml). The organic phasewas then dried over sodium sulfate, filtered, and concentrated to give2-methoxyethyl 2-mercaptoacetate (6.07 g, 84% yield) as a colorless oil.

Delta-damascone (3.00 g, 15.6 mmol), DBU (0.24 ml, 1.6 mmol) andtetrahydrofuran (THF, 20 ml) were heated to 45° C. with stirring. Asolution of 2-methoxyethyl 2-mercaptoacetate (15.6 mmol) in THF (10 ml)was added dropwise. The mixture was stirred for 12 h, cooled to roomtemperature and then concentrated to give a purple oil. The oil wastaken up in dichloromethane (50 ml) and successively washed with aqueousHCl (5%, 2×20 ml), water (2×20 ml), and brine (40 ml). The organic phasewas dried over sodium sulfate, filtered and concentrated to give ayellow oil with 61% yield.

¹³C-NMR: 19.9 (q), 20.7 (q), 21.1/21.3 (q), 29.8 (q), 31.6/31.8 (d),32.8/33.0 (t), 33.1/33.2 (s), 35.3 (d), 41.7 (t), 54.7/54.8 (t), 59.0(q), 62.8/62.9 (d), 64.3 (t), 70.3 (t), 124.1/124.3 (d), 131.7/131.8(d), 170.6 (s), 211.8/212.0 (s).

¹H-NMR: 0.86-0.92 (m, 3H); 0.93-1.01 (m, 6H); 1.29-1.36 (m, 3H);1.65-1.75 (m, 1H); 1.91-2.02 (m, 1H); 2.18-2.25 (m, 1H); 2.45-2.55 (m,1H); 2.72-2.78 (m, 1H); 2.50-2.60 and 2.92-3.00 (2 m, 1H); 3.27-3.38 (m,2H); 3.39 (s, 3H); 3.40-3.50 (m, 1H); 3.58-3.65 (m, 2H); 4.26-4.32 (m,2H); 5.41-5.48 (m, 1H); 5.50-5.58 (m, 1H).

xx) Synthesis of 2,5,8,11-tetraoxamidecan-13-yl2-((4-oxo-4-(2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)acetate

2,5,8,11-Tetraoxamidecan-13-yl 2-mercaptoacetate was synthesized from2,5,8,11-tetraoxamidecan-13-ol (3.00 g, 14.4 mmol) and thioglycolic acid(1.50 ml, 21.7 mmol) as described above (Example xix), yielding acolorless oil (88% yield).

This compound (15.6 mmol) in THF (10 ml) was then added to a solution ofdelta-damascone (3.00 g, 15.6 mmol), DBU (0.24 ml, 1.6 mmol) and THF (20ml) and treated as described above (Example xix) to give the titlecompound with 72% yield.

¹³C-NMR: 19.9 (q), 20.7 (q), 21.1/21.3 (q), 29.8 (q), 31.6/31.8 (d),32.9/33.0 (t), 33.1/33.2 (s), 35.3 (d), 41.7 (t), 54.7/54.8 (t), 59.0(q), 62.8/62.9 (d), 64.4 (t), 69.0 (t), 70.5/70.6 (t), 71.9 (t),124.1/124.3 (d), 131.7/131.8 (d), 170.5/170.8 (s), 211.8/211.9 (s).

¹H-NMR: 0.86-0.92 (m, 3H); 0.93-1.01 (m, 6H); 1.28-1.36 (m, 3H);1.65-1.75 (m, 1H); 1.91-2.02 (m, 1H); 2.17-2.25 (m, 1H); 2.44-2.57 (m,1H); 2.72-2.78 (m, 1H); 2.50-2.60 and 2.91-3.00 (2 m, 1H); 3.27-3.37 (m,2H); 3.38 (s, 3H); 3.40-3.50 (m, 1H); 3.52-3.58 (m, 2H); 3.58-3.69 (m,10H); 3.69-3.76 (m, 2H); 4.26-4.32 (m, 2H); 5.41-5.48 (m, 1H); 5.50-5.58(m, 1H).

xxi) Synthesis of2,5,8,11,14,17,20,23,26,29,32,35-dodecaoxaheptatriacontan-37-yl2-((4-oxo-4-(2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)acetate(average structure)

2,5,8,11,14,17,20,23,26,29,32,35-Dodecaoxaheptatriacontan-37-yl2-mercaptoacetate (average structure) was synthesized from2,5,8,11,14,17,20,23,26,29,32,35-dodecaoxaheptatriacontan-37-ol (averagestructure, M_(n)=500) and thioglycolic acid as described above (Examplexix) with 93% yield.

This compound (15.6 mmol) in THF (10 ml) was then added to a solution ofdelta-damascone (3.00 g, 15.6 mmol), DBU (0.24 ml, 1.6 mmol) and THF (20ml) and treated as described above (Example xix) to give the titlecompound with 88% yield.

¹³C-NMR: 19.9 (q), 20.7 (q), 21.1/21.3 (q), 29.8 (q), 31.6/31.8 (d),31.9 (t), 32.9/33.0 (t), 33.1/33.2 (s), 35.3 (d), 41.7 (t),54.7/54.8/54.9 (t), 59.0 (q), 62.7/62.8/62.9 (t), 64.4/64.9 (t), 68.9(t), 70.5/70.6 (t), 71.9 (t), 124.1/124.3 (d), 131.7/131.8 (d), 170.5(s), 211.8/212.0 (s).

¹H-NMR: 0.84-0.92 (m, 3H); 0.93-1.03 (m, 6H); 1.28-1.38 (m, 3H);1.65-1.75 (m, 1H); 1.91-2.02 (m, 1H); 2.17-2.26 (m, 1H); 2.43-2.57 (m,1H); 2.72-2.79 (m, 1H); 2.50-2.62 and 2.90-3.01 (2 m, 1H); 3.26-3.37 (m,2H); 3.38 (s, 3H); 3.39-3.50 (m, 1H); 3.52-3.59 (m, 2H); 3.59-3.69 (m,40H); 3.69-3.77 (m, 2H); 4.25-4.34 (m, 2H); 5.41-5.48 (m, 1H); 5.50-5.58(m, 1H).

xxii) Synthesis of(ethane-1,2-diylbis(oxy))bis(ethane-2,1-diyl)bis(2-((4-oxo-4-(2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)acetate)

(Ethane-1,2-diylbis(oxy))bis(ethane-2,1-diyl)bis(2-mercaptoacetate) wassynthesized from 2,2′-(ethane-1,2-diylbis(oxy))diethanol (3.61 g, 21.1mmol) and thioglycolic acid (5.00 ml, 72.2 mmol) as described above(Example xix) to give 6.25 g (87% yield) of a colorless oil.

This compound (2.33 g, 7.8 mmol) in THF (10 ml) was then added to asolution of delta-damascone (3.00 g, 15.6 mmol), DBU (0.24 ml, 1.6 mmol)and THF (20 ml) and treated as described above (Example xix) to give thetitle compound in 81% yield.

¹³C-NMR: 19.9 (q), 20.7 (q), 21.1/21.3 (q), 29.8 (q), 31.6/31.8 (d),32.9/33.0 (t), 33.1/33.2 (s), 35.3 (d), 41.7 (t), 54.7/54.8 (t),62.8/62.9 (d), 64.4 (t), 69.0 (t), 70.6 (t), 124.1/124.3 (d),131.7/131.8 (d), 170.5 (s), 211.8/211.9 (s).

¹H-NMR: 0.85-0.92 (m, 6H); 0.93-1.02 (m, 12H); 1.28-1.36 (m, 6H);1.65-1.75 (m, 2H); 1.91-2.02 (m, 2H); 2.18-2.25 (m, 2H); 2.44-2.57 (m,2H); 2.72-2.78 (m, 2H); 2.50-2.60 and 2.91-3.00 (2 m, 2H); 3.27-3.39 (m,4H); 3.39-3.50 (m, 2H); 3.64-3.69 (m, 4H); 3.70-3.75 (m, 4H); 4.26-4.38(m, 4H); 5.41-5.48 (m, 2H); 5.50-5.58 (m, 2H).

xxiii) Synthesis of methyl2-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)acetate

Delta-damascone (10.0 g, 52.0 mmol) and 2-mercaptopropionic acid (5.0 g,47.1 mmol) were stirred for 48 h at room temperature. The reactionmixture was diluted with MTBE (35 ml), washed several times with H₂Othen brine, dried over anhydrous Na₂SO₄, filtered and concentrated undervacuum at a maximum temperature of 50° C. The crude title compound (14.0g), containing some residual delta-damascone, can be used as such. Asample was further purified by flash chromatography on silica gel usinga mixture of MTBE and n-heptane (20% up to 40% in MTBE) as the eluent.

¹³C-NMR: 17.2/17.5 (q), 19.9 (q), 20.7 (q), 21.5/21.8 (q), 29.7/29.8(q), 31.6/31.8 (d), 33.1/33.2 (s), 35.3/35.4 (d), 40.6/41.0 (d),41.7/41.8 (t), 54.5/55.5 (t), 62.8/62.9 (d), 124.1/124.3 (d),131.7/131.8 (d), 179.1/179.5 (s), 211.9/212.6 (s).

¹H-NMR: 0.87-0.93 (m, 3H); 0.93-1.02 (m, 6H); 1.29-1.37 (m, 3H);1.42-1.50 (m, 3H); 1.65-1.74 (m, 1H); 1.93-2.01 (m, 1H); 2.18-2.25 (m,1H); 2.46-2.61 (m, 1.4H); 2.71-2.82 (m, 1H); 2.84-3.08 (m, 0.6H);3.45-3.63 (m, 2H); 5.42-5.48 (m, 1H); 5.51-5.57 (m, 1H); 10.11 (s, 1H).

xxiv) Synthesis of ammonium2-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)propanoate

Delta-damascone (18.2 g, 95 mmol) and ammonium 2-mercaptopropanoate (58%aqueous solution; 16.8 g, 79 mmol) were stirred for 17 h at roomtemperature. The reaction mixture was diluted with water (20 ml), thenextracted with MTBE (3×30 ml). Remaining starting material was recoveredfrom the combined organic phases by removing the solvent under reducedpressure. The aqueous phase containing the target ammonium carboxylatewas concentrated under vacuum yielding 21.2 g of the target compound asa white semi-crystalline material (71% yield).

¹³C-NMR: 18.3/18.4 (q), 19.3/19.4 (q), 20.5 (q), 21.0/21.3 (q), 29.1(q), 30.9/31.2 (d), 32.4/32.5 (s), 33.6/33.7 (d), 40.9/41.0 (t),42.2/42.5 (d), 54.4/54.5 (t), 61.2/61.4 (d), 124.0/124.2 (d),131.5/131.6 (d), 174.9/175.0 (s), 212.1 (s).

¹H-NMR: 0.81-0.87 (m, 6H); 0.92-0.97 (m, 3H); 1.15-1.21 (m, 3H);1.22-1.27 (m, 3H); 1.61-1.70 (m, 1H); 1.91-2.01 (m, 1H); 2.24-2.41 (m,2H); 2.49-2.53 (m, 1H); 2.53-3.02 (m, 2H); 3.27-3.37 (m, 2H); 5.41-5.47(m, 1H); 5.50-5.56 (m, 1H); 7.40 (broad, NH₄).

xxv) Synthesis of3-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)propanoicacid

Delta-damascone (41.0 g, 213 mmol) and 3-mercaptopropanoic acid (15.0 g,141 mmol) were stirred at room temperature for 68 h. The viscousreaction mixture was diluted with MTBE (35 ml), washed several timeswith H₂O then brine, dried over anhydrous Na₂SO₄, filtered andconcentrated under vacuum at a maximum temperature of 50° C. The crudetitle compound (49.0 g), containing some residual delta-damascone, canbe used as such. A sample was further purified by flash chromatographyon silica gel using a mixture of MTBE and n-heptane (20% up to 50% inMTBE) as the eluent.

¹³C-NMR: 19.9/20.0 (q), 20.7 (q), 21.6/21.8 (q), 25.4/25.6 (t), 29.8(q), 31.6/31.8 (d), 33.1/33.2 (s), 34.4/34.5 (d), 34.7 (t), 41.7/41.8(t), 55.0/55.1 (t), 62.9/63.0 (d), 124.1/124.3 (d), 131.8/131.8 (d),177.9 (s), 212.2/212.3 (s).

¹H-NMR: 0.87-0.92 (m, 3H); 0.94-1.00 (m, 6H); 1.29-1.34 (m, 3H);1.66-1.74 (m, 1H); 1.93-2.01 (m, 1H); 2.18-2.24 (m, 1H); 2.47-2.58(1.5H); 2.65-2.75 (m, 3H); 2.79-2.85 (m, 2H); 2.88-2.95 (m, 0.5H);3.28-3.38 (m, 1H); 5.42-5.48 (m, 1H); 5.51-5.57 (m, 1H); 11.25 (s, 1H).

xxvi) Synthesis of trimethylsilyl3-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)propanoate

Using the same experimental procedure as described in Example v, thetitle compound was obtained from the acid described above (Example xxv).

¹³C-NMR: −0.2 (q), 19.9/20.0 (q), 20.8 (q), 21.6/21.8 (q), 25.8/25.9(t), 29.8 (q), 31.6/31.8 (d), 33.1/33.2 (s), 34.3/34.4 (d), 36.4 (t),41.8 (t), 55.1/55.2 (t), 62.9/63.0 (d), 124.1/124.2 (d), 131.8/131.9(d), 172.4 (s), 212.2/212.3 (s).

¹H-NMR: 0.29 (s, 9H); 0.87-0.91 (m, 3H); 0.94-1.00 (m, 6H); 1.29-1.33(m, 3H); 1.65-1.74 (m, 1H); 1.92-2.01 (m, 1H); 2.18-2.24 (m, 1H);2.46-2.57 (m, 1.5H); 2.58-2.64 (m, 2H); 2.70-2.73 (m, 1H); 2.75-2.81 (m,2H); 2.87-2.94 (m, 0.5H); 3.27-3.37 (m, 1H); 5.41-5.48 (m, 1H);5.51-5.57 (m, 1H).

xxvii) Synthesis of methyl3-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)propanoate

DBU (2.0 g) was added during 2 min to a mixture of delta-damascone (32.0g, 166 mmol) and methyl 3-mercaptopropionate (15.0 g, 125 mmol). After 2h, the reaction was quenched with aqueous citric acid. The reactionmixture was diluted with MTBE (15 ml), washed with H₂O and brine, driedover anhydrous Na₂SO₄, filtered and concentrated under high vacuum at amaximum temperature of 50° C. The resulting mixture of the targetcompound (75%) and delta-damascone (23%) can be used as such. A puresample (98%; two diastereoisomers ca. 1:1) was obtained byflash-chromatography (heptane/MTBE 95:5) on SiO₂.

¹³C-NMR: 19.9 (q), 20.7 (q), 21.6/21.8 (q), 25.7/25.9 (t), 29.8 (q),31.6/31.8 (d), 33.1/33.2 (s), 34.3 (d), 34.7 (t), 41.7 (t), 51.8 (q),55.0/55.1 (t), 62.9/63.0 (d), 124.1/124.3 (d), 131.7/131.8 (d), 172.3(s), 212.1/212.2 (s).

¹H-NMR: 0.87-0.92 (m, 3H); 0.94-1.01 (m, 6H); 1.29-1.33 (m, 3H);1.66-1.74 (m, 1H); 1.93-2.01 (m, 1H); 2.18-2.24 (m, 1H); 2.47-2.95 (m,7H); 3.27-3.37 (m, 1H); 3.70 (s, 3H), 5.42-5.48 (m, 1H); 5.50-5.58 (m,1H).

xxviii) Synthesis of methyl3-(((5S)-2-methyl-3-oxo-5-(prop-1-en-2-yl)cyclohexyl)thio)propanoate

This compound was prepared from(R)-2-methyl-5-(prop-1-en-2-yl)cyclohex-2-enone (carvone gauche; 28.1 g,187 mmol), DBU (0.25 g) and methyl 3-mercaptopropionate (27.0 g, 225mmol) according to the procedure described above (Example xxvii). Theresulting crude material (53.2 g), containing some residual carvone canbe used as such. Further purification by vacuum distillation (132-140°C., 0.1 mbar) afforded 35.1 g (69% yield) of the pure title compound.

¹³C NMR: 12.6 (q), 20.8 (q), 27.0 (t), 34.6 (t), 35.9 (t), 40.7 (d),46.0 (t), 48.6 (d), 50.2 (d), 51.8 (q), 110.3 (t), 147.0 (s), 172.1 (s),209.5 (s).

¹H-NMR: 1.15 (d, J=6.7, 3H); 1.76 (s, 3H); 1.97-2.07 (m, 1H); 2.15-2.29(m, 2H); 2.44-2.51 (m, 1H); 2.56-2.63 (m, 2H); 2.74-2.85 (m, 3H);2.85-2.96 (m, 1H); 3.42-3.48 (m, 1H); 3.70 (s, 3H); 4.71-4.86 (m, 2H).

xxix) Synthesis of methyl3-((4,4-dimethyl-2-(pent-4-enoyl)cyclohexyl)thio)propanoate (mainisomer)

This compound was prepared from a mixture of 1-(5,5- and3,3-dimethylcyclohex-1-enyl)pent-4-en-1-one (Neobutenone®; origin:Firmenich SA; 8.0 g, 41.6 mmol), DBU (0.06 g) and methyl3-mercaptopropionate (5.0 g, 41.6 mmol) according to the proceduredescribed above (Example xxvii). The resulting crude material (14.0 g),containing the target compound (75%; isomer ratio cis/trans ca. 1:1),10% of other regioisomers, as well as some residual Neobutenone®, can beused as such. Further purification by vacuum distillation (bulb to bulbdistillation, 137-140° C., 0.1 mbar) afforded 8.7 g (67% yield) of titlecompound (also containing ca. 10% of other regioisomers).

¹³C-NMR (major isomers): 24.2/24.4 (q), 26.4/27.2 (t), 27.3/27.6 (t),28.0/30.2 (t), 30.0/30.1 (s), 32.4/32.8 (q), 33.1/34.7 (t), 34.9/35.6(t), 38.9/39.4 (t), 42.5/42.8 (t), 44.6/45.3 (d), 50.2/52.2 (d),51.7/51.8 (q), 115.0/115.1 (t), 137.3/137.5 (d), 172.3 (s), 210.1/212.0(s).

¹H-NMR (major isomers): 0.85-1.02 (m, 6H); 1.06-2.03 (m, 6H); 2.28-2.38(m, 2H); 2.45-2.82 (m, 8H); 3.67-3.71 (m, 3H); 4.94-5.10 (m, 2H);5.75-5.90 (m, 1H).

xxx) Synthesis of methyl3-((7-(pent-4-enoyl)spiro[4.5]decan-8-yl)thio)propanoate-methyl3-((7-(pent-4-enoyl)spiro[4.5]decan-6-yl)thio)propanoate (mixture)

This compound was prepared from a mixture of 1-(spiro[4.5]dec-7- and6-en-7-yl)pent-4-en-1-one (Spirogalbanone®; origin: Givaudan SA), DBUand methyl 3-mercaptopropionate according to the procedure describedabove (Example xxvii).

¹³C-NMR (major isomers): 23.9/24.0 (t), 24.9/25.0 (t), 26.4/27.2 (t),27.3/27.6 (t), 29.2/30.4 (t), 31.5/31.9 (t), 34.5/34.6 (t), 34.7/34.9(t), 37.6/39.3 (t), 41.6 (t), 41.9/42.2 (s), 42.1/42.4 (t), 44.6/45.3(d), 51.6/53.5 (d), 51.7/51.8 (q), 115.0/115.1 (t), 137.3/137.5 (d),172.3 (s), 210.2/211.9 (s).

¹H-NMR (major isomers): 1.18-1.81 (m, 14H); 1.82-2.06 (m, 1H); 2.28-2.37(m, 2H); 2.46-2.69 (m, 5H); 2.70-2.82 (m, 2H); 3.66-3.69 (m, 3H);4.94-5.08 (m, 2H); 5.76-5.90 (m, 1H).

xxxi) Synthesis of methyl3-(((1S,1′R,5R)-2,6,6-trimethyl-4′-oxospiro[bicyclo[3.1.1]heptane-3,1′-cyclohexan]-2′-yl)thio)propanoate

This compound was prepared from(1S,1′S,2S,5R)-2,6,6-trimethylspiro[bicycle[3.1.1]heptane-3,1′-cyclohex[2]en]-4′-one(Wolfwood®; origin: Firmenich SA), DBU and methyl 3-mercaptopropionateaccording to the procedure described above (Example xxvii).

¹³C-NMR: 18.8/19.8 (q), 23.6/23.9 (q), 26.3/26.7 (t), 27.0/27.3 (q),27.1/27.4 (t), 27.4 (q), 34.1/34.6 (t), 36.3 (s), 37.2/37.8 (t),38.8/39.1 (s), 40.4 (d), 41.4 (t), 41.5/41.6 (d), 43.3/44.0 (t), 46.0(t), 51.0/51.8 (d), 51.8/54.1 (d), 172.2 (s), 209.0/209.4 (s).

¹H-NMR: 0.93-1.11 (m, 3H); 1.17-1.27 (m, 4H); 1.28-1.46 (m, 3H);1.58-1.91 (m, 1H); 1.91-2.18 (m, 5H); 1.92-2.55 (m, 4H); 2.55-2.70 (m,3H); 2.71-2.90 (m, 2H); 2.91-3.08 (m, 1H); 3.12-3.16 (m, 0.5H);3.48-3.52 (m, 0.5H); 3.68-3.71 (m, 3H).

xxxii) Synthesis of methyl3-((3,7-dimethyl-1-oxooct-6-en-3-yl)thio)propanoate

This compound was prepared from (E)-3,7-dimethylocta-2,6-dienal (citral;10.0 g, 65.7 mmol), DBU (0.1 g) and methyl 3-mercaptopropionate (7.9 g,65.7 mmol) according to the procedure described above (Example xxvii).The resulting crude material (19.5 g), containing some residual citralcan be used as such. Further purification by vacuum distillation (bulbto bulb distillation, 132-140° C., 0.1 mbar) afforded 12.5 g (70% yield)of pure title compound (97%).

¹³C-NMR: 17.7 (q), 22.5 (t), 22.8 (t), 25.7 (q), 26.2 (q), 34.0 (t),40.8 (t), 46.4 (s), 51.8 (q), 52.4 (t), 123.3 (d), 132.3 (s), 172.1 (s),201.3 (d).

¹H-NMR: 1.42 (s, 3H); 1.60-1.70 (m, 8H); 2.03-2.17 (m, 2H); 2.53-2.60(m, 4H); 2.74-2.80 (m, 2H); 3.70 (s, 3H); 5.05-5.11 (m, 1H); 9.83-9.86(m, 1H).

xxxiii) Synthesis of methyl 3-((2-formyl-1-phenyloctyl)thio)propanoate

This compound was prepared from (E)-2-benzylideneoctanal (hexylcinnamicaldehyde; origin: Firmenich SA), DBU and methyl 3-mercaptopropionateaccording to the procedure described above (Example xxvii).

¹³C-NMR: 14.0 (q), 22.4/22.5 (t), 26.0/26.2 (t), 26.5/26.8 (t),27.4/28.4 (t), 29.0/29.2 (t), 31.4/31.5 (t), 34.2 (t), 49.8/50.5 (d),51.8 (q), 56.5/56.8 (d), 127.7/127.8 (d); 128.4 (2d), 128.7 (2d), 139.6(s), 172.1 (s), 202.0/202.6 (d).

¹H-NMR: 0.77-0.90 (m, 3H); 1.05-1.34 (m, 9H); 1.38-1.78 (m, 1H);2.37-2.48 (m, 2H); 2.52-2.68 (m, 3H); 3.62-3.66 (m, 3H); 3.94-4.17 (m,1H); 7.22-7.38 (m, 5H); 9.51-9.62 (m, 1H).

xxxiv) Synthesis of methyl3-((1-cyano-2,6-dimethyloct-5-en-2-yl)thio)propanoate, (Z/E) isomericmixture

This compound was prepared from 3,7-dimethylnona-2,6-dienenitrile(Lemonile®; origin: Givaudan SA), DBU and methyl 3-mercaptopropanoate,according to the procedure described above (Example xxvii).

¹³C-NMR (deduced from the mixture): major (E), 55% of the mixture, 12.7(q), 16.0 (q), 22.8 (t), 22.9 (t), 25.8 (q), 30.8 (t), 32.3 (t), 34.0(t), 39.7 (t), 46.3 (s), 51.9 (q), 117.1 (s), 121.3 (d), 138.1 (s),172.1 (s); minor (Z), 45% of the mixture, 12.8 (q), 16.0 (q), 22.7 (t),24.8 (t), 25.8 (q), 30.8 (2t), 34.0 (t), 39.9 (t), 46.3 (s), 51.9 (q),117.1 (s), 122.5 (d), 138.4 (s), 170.9 (s).

¹H-NMR: 0.95-1.01 (m, 3H); 1.41-1.45 (m, 3H); 1.61-1.63 (m, 2H);1.64-1.71 (m, 3H); 1.94-2.19 (m, 4H); 2.55-2.61 (m, 2H); 2.64-2.67 (m,2H); 2.76-2.72 (m, 2H); 3.71 (s, 3H); 5.01-5.12 (m, 1H).

xxxv) Synthesis of methyl 3-((2-cyano-1-phenylethyl)thio)propanoate

This compound was prepared from cinnamonitrile, DBU and methyl3-mercaptopropionate according to the procedure described above (Examplexxvii).

¹³C-NMR: 25.6 (t), 26.6 (t), 34.1 (t), 45.7 (d), 51.9 (q), 117.1 (s),127.4 (2d), 128.5 (d), 129.1 (2d), 139.0 (s), 171.9 (s).

¹H-NMR: 2.48-2.53 (m, 2H); 2.65-2.71 (m, 2H); 2.85-2.91 (m, 2H); 3.66(s, 3H); 4.12-4.19 (m, 1H); 7.28-7.35 (m, 1H); 7.35-7.39 (m, 4H).

xxxvi) Synthesis of methyl3-((1-cyano-1-phenylpentan-2-yl)thio)propanoate

This compound (ca. 1:1 mixture of diastereoisomers) was prepared from2-phenylhex-2-enenitrile (Salicynile®; origin: Firmenich SA) and methyl3-mercaptopropanoate, according to the procedure described above(Example xxvii).

¹³C-NMR: 13.6 (q), 20.1/20.2 (t), 26.9/27.5 (t), 33.5/34.7 (t),34.8/36.0 (t), 44.6/44.7 (d), 50.8/51.4 (d), 51.8/51.9 (q), 119.1/119.2(s), 128.2 (d), 128.3 (d), 128.4/128.5 (d), 128.8 (d), 128.9 (d),133.7/133.8 (s), 172.0/172.1 (s).

¹H-NMR: 0.82-0.94 (m, 3H); 1.22-1.72 (m, 4H); 2.37-2.59 (m, 3H);2.65-2.71 (m, 1H); 2.88-2.97 (m, 1H); 3.64-3.71 (m, 3H); 4.08-4.16 (m,1H); 7.33-7.42 (m, 5H).

xxxvii) Synthesis of methyl3-((1-(cyano(phenyl)methyl)cyclohexyl)thio)propanoate

This compound was prepared from 2-cyclohexylidene-2-phenylacetonitrile(Peonile®; origin: Givaudan SA) and methyl 3-mercaptopropanoate,according to the procedure described above (Example xxvii).

¹³C-NMR: 21.5 (t), 21.6 (t), 22.6 (t), 25.2 (t), 33.0 (t), 33.4 (t),33.7 (t), 50.8 (d), 51.8 (q), 52.6 (s), 119.7 (s), 128.3 (2d), 128.5(d), 130.1 (2d), 132.0 (s), 172.1 (s).

¹H-NMR: 1.04-1.82 (m, 10H); 2.33-2.53 (m, 4H); 3.69 (s, 3H); 3.95 (s,1H); 7.34-7.43 (m, 5H).

xxxviii) Synthesis of butyl3-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)propanoate

This compound was prepared from delta-damascone, DBU and butyl3-mercaptopropionate according to the procedure described above (Examplexxvii).

¹³C-NMR: 13.7 (q), 19.2 (t), 19.9 (q), 20.8 (q), 21.6/21.8 (q),25.8/25.9 (t), 29.8 (q), 30.6 (t), 31.6/31.8 (d), 33.1/33.2 (s), 34.3(d), 34.9 (t), 41.7 (t), 51.8 (q), 55.0/55.2 (t), 62.9 (d), 64.8 (t),124.1/124.3 (d), 131.7/131.8 (d), 172.0 (s), 212.1/212.2 (s).

¹H-NMR: 0.87-1.01 (m, 12H); 1.29-1.33 (m, 3H); 1.33-1.44 (m, 2H);1.58-1.66 (m, 2H); 1.66-1.74 (m, 1H); 1.93-2.01 (m, 1H); 2.18-2.24 (m,1H); 2.47-2.64 (m, 4H); 2.69-2.73 (m, 1H); 2.77-2.84 (m, 2H); 3.27-3.37(m, 1H); 4.07-4.13 (m, 2H); 5.42-5.48 (m, 1H); 5.50-5.58 (m, 1H).

xxxix) Synthesis of 2-ethylhexyl3-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)propanoate

This compound was prepared from delta-damascone, DBU and 2-ethylhexyl3-mercaptopropanoate according to the procedure described above (Examplexxvii).

¹³C-NMR: 11.0 (q), 14.0 (q), 19.9 (q), 20.7 (q), 21.6/21.8 (q), 23.0(t), 23.8 (t), 25.8/25.9 (t), 28.9 (t), 29.8 (q), 30.4 (t), 31.6/31.8(d), 33.1/33.2 (s), 34.3 (d), 34.9 (t), 38.7 (d), 41.7 (t), 55.0/55.1(t), 62.8/62.9 (d), 67.1 (t), 124.1/124.3 (d), 131.8 (d), 172.1 (s),212.1/212.2 (s).

¹H-NMR: 0.87-0.92 (m, 9H); 0.94-1.01 (m, 6H); 1.26-1.40 (m, 11H);1.53-1.61 (m, 2H); 1.65-1.74 (m, 1H); 1.92-2.01 (m, 1H); 2.18-2.24 (m,1H); 2.46-2.58 (m, 1H); 2.58-2.65 (m, 2H); 2.70-2.74 (m, 1H); 2.78-2.84(m, 2H); 3.28-3.37 (m, 1H); 3.99-4.05 (m, 2H); 5.41-5.48 (m, 1H);5.50-5.58 (m, 1H).

xl) Synthesis of octadecyl3-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)propanoate

This compound was prepared from delta-damascone, DBU and stearylmercaptopropionate according to the procedure described above (Examplexxvii).

¹³C-NMR: 14.1 (q), 19.9 (q), 20.7 (q), 21.6/21.8 (q), 22.7 (t), 25.8(t), 28.6 (t), 29.3 (t), 29.4 (t), 29.7 (t), 29.5 (t), 29.6 (t),29.6/29.7 (8t), 29.8 (q), 31.6/31.8 (d), 31.9 (t), 33.1/33.2 (s), 34.3(d), 34.9 (t), 41.7 (t), 55.1/55.2 (t), 62.9/63.0 (d), 64.9 (t),124.1/124.2 (d), 131.7/131.8 (d), 172.0 (s), 212.1/212.2 (s).

¹H-NMR: 0.87-0.92 (m, 6H); 0.93-1.01 (m, 6H); 1.21-1.37 (m, 33H);1.57-1.65 (m, 2H); 1.65-1.74 (m, 1H); 1.93-2.01 (m, 1H); 2.18-2.24 (m,1H); 2.47-2.57 (m, 2H); 2.57-2.64 (m, 2H); 2.69-2.73 (m, 1H); 2.78-2.84(m, 2H); 3.27-3.37 (m, 1H); 4.05-4.12 (m, 2H); 5.42-5.48 (m, 1H);5.50-5.58 (m, 1H).

xli) Synthesis of(S,R)-2-ethyl-2-(((3-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)propanoyl)oxy)methyl)propane-1,3-diylbis(3-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)propanoate)

Delta-damascone (29.0 g, 151 mmol), DBU (1.0 g) and2-ethyl-2-((3-mercaptopropanoyloxy)methyl)propane-1,3-diylbis(3-mercaptopropanoate) (10.0 g, 25.1 mmol) were stirred for 16 h atroom temperature. The reaction mixture was diluted with MTBE (15 ml),washed with aqueous citric acid, with water and brine, dried overanhydrous Na₂SO₄, filtered and then concentrated under high vacuum at amaximum temperature of 50° C. The resulting mixture (33.0 g) containingdelta-damascone, the target compound (main ingredient),(S,R)-2-ethyl-2-(((3-mercaptopropanoyl)oxy)methyl)propane-1,3-diylbis(3-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)propanoate)and2-ethyl-2-(((3-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)propanoyl)oxy)methyl)propane-1,3-diylbis(3-mercaptopropanoate) can be used as such. A pure sample (90%) ofthe title compound was obtained by flash-chromatography (heptane/MTBE70:30) on SiO₂.

¹³C-NMR: 7.4 (q), 19.9/20.0 (q), 20.7 (q), 21.6/21.8 (q), 22.9 (t),25.7/25.9 (t), 29.8 (q), 31.6/31.8 (d), 33.1/33.2 (s), 34.4 (d), 34.8(t), 40.8 (s), 41.7 (t), 55.0/55.1 (t), 62.8/62.9 (d), 63.9 (t),124.1/124.3 (d), 131.7/131.8 (d), 171.5 (s), 212.1/212.2 (s).

¹H-NMR: 0.86-0.92 (m, 12H); 0.93-1.00 (m, 18H); 1.28-1.32 (m, 9H);1.46-1.53 (m, 2H); 1.65-1.74 (m, 3H); 1.93-2.01 (m, 3H); 2.18-2.24 (m,3H); 2.46-2.94 (m, 21H); 3.26-3.36 (m, 3H); 4.06 (s, 6H); 5.42-5.48 (m,3H); 5.50-5.57 (m, 3H).

xlii) Synthesis of(S,R)-2,2-bis(((3-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)propanoyl)oxy)methyl)propane-1,3-diylbis(3-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)propanoate)

Delta-damascone (24.0 g, 125 mmol), DBU (0.5 g) and pentaerythritoltetra(3-mercaptopropionate) (10.0 g, 20.5 mmol) were stirred for 4 h atroom temperature. The reaction mixture was diluted with MTBE (15 ml),washed with aqueous citric acid, with water (3×10 ml) and brine (10 ml),dried over anhydrous Na₂SO₄, filtered and then concentrated under highvacuum at a maximum temperature of 50° C. The resulting mixture (26.9 g)containing delta-damascone, the target compound (main ingredient),(S,R)-2-(((3-mercaptopropanoyl)oxy)methyl)-2-(((3-((4-oxo-4-((1S,2R)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)propanoyl)oxy)methyl)propane-1,3-diylbis(3-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)propanoate),2,2-bis(((3-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)propanoyl)oxy)methyl)propane-1,3-diylbis(3-mercaptopropanoate) and2-(((3-mercaptopropanoyl)oxy)methyl)-2-(((3-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)propanoyl)oxy)methyl)propane-1,3-diylbis(3-mercaptopropanoate) can be used as such. A sample was furtherpurified by flash chromatography on silica gel using a mixture of MTBEand n-heptane (20% up to 30% in MTBE) as the eluent.

¹³C-NMR: 19.9/20.0 (q), 20.7 (q), 21.6/21.8 (q), 25.7/25.8 (t), 29.8(q), 31.6/31.8 (d), 33.1/33.2 (s), 34.5 (d), 34.7 (t), 41.7 (t), 42.1(s), 55.0/55.1 (t), 62.2 (t), 62.8/62.9 (d), 124.1/124.3 (d),131.7/131.8 (d), 171.5 (s), 212.1/212.2 (s).

¹H-NMR: 0.86-0.92 (m, 12H); 0.93-1.00 (m, 24H); 1.29-1.33 (m, 12H);1.65-1.74 (m, 4H); 1.93-2.01 (m, 4H); 2.18-2.24 (m, 4H); 2.46-2.94 (m,28H); 3.26-3.36 (m, 4H); 4.16 (s, 8H); 5.42-5.48 (m, 4H); 5.50-5.57 (m,4H).

xliii) Synthesis ofN,N-dimethyl-3-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)propanamide

Delta-damascone (4.39 g, 22.8 mmol), S-3-(dimethylamino)-3-oxopropylethanethioate (4.0 g, 22.8 mmol) and DBU (0.17 g, 1.1 mmol) weredissolved in methanol (3.7 ml) and stirred for 4.5 h at roomtemperature. The reaction mixture was diluted with MTBE (15 ml), washedfirst with aqueous citric acid, then with water and concentrated undervacuum (at a maximum temperature of 50° C. The crude title compound (8.0g, ca. 1:1 diasteroisomeric mixture) still contains some residualdelta-damascone (12%). It can be used as such. A sample was furtherpurified by flash-distillation (bulb to bulb distillation; 195-200° C.,0.1 mbar).

¹³C-NMR: 19.9/20.0 (q), 20.7 (q), 21.5/21.7 (q), 25.8/25.9 (t), 29.8(q), 31.6/31.8 (d), 33.1/33.2 (s), 33.6 (t), 34.3 (d), 35.4 (q), 37.1(q), 41.7 (t), 55.0/55.1 (t), 62.8/62.9 (d), 124.1/124.3 (d),131.7/131.8 (d), 171.1 (s), 212.3 (s).

¹H-NMR: 0.87-0.92 (m, 3H); 0.93-1.01 (m, 6H); 1.29-1.34 (m, 3H);1.65-1.73 (m, 1H); 1.92-2.01 (m, 1H); 2.18-2.25 (m, 1H); 2.46-2.64 (m,3.5H); 2.70-2.75 (m, 1H); 2.81-2.88 (m, 2H); 2.88-2.93 (m, 0.5H);0.2.94-2.99 (m, 3H); 2.99-3.05 (m, 3H); 3.28-3.37 (m, 1H); 5.42-5.48 (m,1H); 5.50-5.58 (m, 1H).

xliv) Synthesis ofN,N-dimethyl-3-(((5S)-2-methyl-3-oxo-5-(prop-1-en-2-yl)cyclohexyl)thio)propanamide

This compound was prepared from carvone gauche (3.70 g, 22.8 mmol),S-3-(dimethylamino)-3-oxopropyl ethanethioate and DBU in methanol,according to the procedure described above (Example xliii). The crudematerial, containing some residual carvone, can be used as such.Purification by chromatography (SiO₂, heptane/MTBE 80:20 to 20:80)yielded 2.5 g of the pure target compound (97% by GC).

¹³C-NMR: 12.6 (q), 20.3 (q), 25.7 (t), 33.7 (t), 35.5 (q), 37.1 (q),39.4 (t), 44.3 (d), 46.4 (t), 49.7 (d), 50.6 (d), 110.3 (t), 146.5 (s),170.9 (s), 209.7 (s).

¹H-NMR: 1.23 (d, J=6.5, 3H); 1.75 (s, 3H); 1.78-1.91 (m, 1H); 2.29-2.40(m, 4H); 2.42-2.50 (m, 1H); 2.53-2.63 (m, 3H); 2.87-2.94 (m, 2H); 2.96(s, 3H); 3.02 (s, 3H); 4.74-4.81 (m, 2H).

xlv) Synthesis of3-((3,7-dimethyl-1-oxooct-6-en-3-yl)thio)-N,N-dimethylpropanamide

This compound was prepared from citral (4.2 g, 27.6 mmol),S-3-(dimethylamino)-3-oxopropyl ethanethioate and DBU in methanol,according to the procedure described above (Example xliii). The crudematerial, containing some residual citral, can be used as such.Purification by chromatography (SiO₂, heptane/MTBE 90:10) yielded 2.0 gof the pure target compound (>99% by NMR, partial decomposition on GC).

¹³C-NMR: 17.7 (q), 22.8 (t), 22.9 (t), 25.6 (q), 26.2 (q), 33.0 (t),35.4 (q), 37.1 (q), 40.9 (t), 46.4 (s), 52.4 (t), 123.4 (d), 132.2 (s),170.9 (s), 201.6 (d).

¹H-NMR: 1.42 (s, 3H); 1.60-1.70 (m, 8H); 2.00-2.24 (m, 2H); 2.50-2.63(m, 4H); 2.78-2.85 (m, 2H); 2.95 (s, 3H); 2.99 (s, 3H); 5.05-5.11 (m,1H); 9.83-9.86 (m, 1H).

xlvi) Synthesis of3-((2-cyano-1-phenylethyl)thio)-N,N-dimethylpropanamide

This compound was prepared from cinnamonitrile (4.0 g, 22.8 mmol),S-3-(dimethylamino)-3-oxopropyl ethanethioate and DBU in methanol,according to the procedure described above (Example xliii). The crudematerial (6.1 g, containing ca. 30% cinnamonitrile) can be used as such.Purification by flash-distillation (bulb to bulb distillation, 220-225°C., 0.1 mbar) gave 4.1 g of a yellow oil, 95% pure by GC (68% yield).

¹³C-NMR: 25.6 (t), 27.1 (t), 33.4 (t), 35.4 (q), 37.0 (q), 46.0 (d),117.3 (s), 127.4 (2d), 128.4 (d), 129.0 (2d), 139.5 (s), 170.6 (s).

¹H-NMR: 2.43-2.50 (m, 2H); 2.72-2.78 (m, 2H); 2.87-2.93 (m, 8H);4.15-4.20 (m, 1H); 7.27-7.33 (m, 1H); 7.33-7.41 (m, 4H).

xlvii) Synthesis of2-methyl-3-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)propanoicacid

Delta-damascone (9.0 g, 46.8 mmol) and 3-mercapto-2-methylpropanoic acid(5.0 g, 41.6 mmol) were stirred for 72 h at room temperature. Thereaction mixture was diluted with MTBE (30 ml), washed several timeswith H₂O and concentrated under vacuum at a maximum temperature of 50°C. The crude title compound (14.5 g), containing some residualdelta-damascone, can be used as such. Further purification by flashchromatography on silica gel using a mixture of MTBE and n-heptane (20%up to 40% in MTBE) as the eluent afforded 10.5 g (yield 81%) of 95% puretarget compound.

¹³C-NMR: 16.6/16.8 (q), 19.9 (q), 20.7 (q), 21.6/21.9 (q), 29.8 (q),31.6/31.8 (d), 33.1/33.2 (s), 33.8/34.0 (t), 34.7/34.9 (d), 40.1/40.3(d), 41.7 (t), 55.1/55.2 (t), 62.9/62.9 (d), 124.1/124.3 (d),131.7/131.8 (d), 181.3/181.5 (s), 212.2/212.4 (s).

¹H-NMR: 0.86-0.92 (m, 3H); 0.93-1.02 (m, 6H); 1.26-1.34 (m, 6H);1.65-1.74 (m, 1H); 1.93-2.01 (m, 1H); 2.18-2.25 (m, 1H); 2.46-2.58 (m,1.4H); 2.58-2.66 (m, 1H); 2.69-2.76 (m, 2H); 2.86-2.94 (m, 1H);2.94-2.96 (m, 0.6H); 3.25-3.37 (m, 1H); 5.42-5.48 (m, 1H); 5.51-5.57 (m,1H); 11.05 (s, 1H).

xlviii) Synthesis of2-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)succinicacid

Delta-damascone (23.0 g, 120 mmol), mercaptosuccinic acid (6.0 g, 40mmol) and dimethylsulfoxide (DMSO; 20 ml) were stirred for 93 h at roomtemperature. The solvent and the excess of delta-damascone were removedby vacuum distillation (bulb to bulb distillation, 90-140° C., 0.1 mbar)to yield the title compound (7.5 g, 55% yield). The resulting 95% purematerial can be used as such.

¹³C-NMR: 19.9 (q), 20.7 (q), 21.5/21.9 (q), 29.8 (q), 31.6/31.8 (d),33.1/33.2 (t), 35.9/36.2 (d), 36.5 (t), 40.8/41.3 (d), 41.7 (t),54.3/55.2 (t), 62.8/62.9 (d), 124.1/124.3 (d), 131.7/131.8 (d),176.7/176.8 (s), 177.8/178.1 (s), 211.9/212.5 (s).

¹H-NMR: 0.85-0.92 (m, 3H); 0.92-1.02 (m, 6H); 1.33-1.39 (m, 3H);1.66-1.74 (m, 1H); 1.93-2.01 (m, 1H); 2.19-2.25 (m, 1H); 2.46-2.58 (m,1H); 2.70-3.09 (m, 4H); 3.51-3.63 (m, 1H); 3.67-3.84 (m, 1H); 5.42-5.48(m, 1H); 5.50-5.58 (m, 1H); 11.47 (s, 2H).

xlix) Synthesis of4-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)butanoicacid

Delta-damascone (3.0 g, 15.6 mmol) and 4-mercaptobutanoic acid (2.0 g,16.6 mmol) were stirred for 5 d at room temperature. Unreacted startingmaterial, as well as dihydrothiophen-2(3H)-one, generated as aby-product, was removed by vacuum distillation (bulb to bulbdistillation, 90-140° C., 0.1 mbar) to yield the title compound (0.6 g,ca. 1:1 diastereoisomeric mixture, 12% yield).

¹³C-NMR: 19.9/20.0 (q), 20.8 (q), 21.6/21.8 (q), 24.5 (t), 29.8 (q),30.0/30.1 (t), 31.6/31.8 (d), 32.8 (t), 33.1/33.2 (s), 34.0/34.1 (d),41.8 (t), 55.1/55.2 (t), 62.9/63.0 (d), 124.1/124.3 (d), 131.7/131.8(d), 179.4 (s), 212.4/212.5 (s).

¹H-NMR: 0.87-0.92 (m, 3H); 0.94-1.00 (m, 6H); 1.27-1.33 (m, 3H);1.66-1.74 (m, 1H); 1.88-2.08 (m, 3H); 2.18-2.24 (m, 1H); 2.47-2.78 (m,7H); 3.26-3.36 (m, 1H); 5.42-5.48 (m, 1H); 5.51-5.58 (m, 1H); 11.23 (s,1H).

1) Synthesis of trimethylsilyl4-((4-oxo-4-((1RS,2SR)-2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)thio)butanoate

Using the experimental procedure described above (Example v) the titlecompound was obtained from the acid described above (Example xlix).

¹³C-NMR: −0.22 (q), 19.8/19.9 (q), 20.7 (q), 21.6/21.8 (q), 24.9/25.0(t), 29.8 (q), 30.0/30.1 (t), 31.6/31.8 (d), 33.1/33.2 (s), 34.1 (d),34.7 (t), 41.8 (t), 55.1/55.2 (t), 62.8/62.9 (d), 124.1/124.2 (d),131.8/131.9 (d), 173.6 (s), 212.2/212.3 (s).

¹H-NMR: 0.29 (s, 9H); 0.87-0.92 (m, 3H); 0.94-1.01 (m, 6H); 1.27-1.32(m, 3H); 1.66-1.74 (m, 1H); 1.84-2.03 (m, 3H); 2.18-2.24 (m, 1H);2.40-2.62 (m, 6H); 2.68-2.73 (m, 1H); 3.25-3.35 (m, 1H); 5.42-5.48 (m,1H); 5.51-5.58 (m, 1H).

Example 2 Performance of a Softener Base Comprising an Invention'sCompound of Formula (I) as Compared to the Prior-Art

The liberation of delta-damascone from the present invention's compoundsof formula (I) was tested in a fabric softening surfactant emulsion withthe following final composition:

Stepantex ® VL90 A (origin: Stepan) 16.5% by weight Calcium chloride(10% aq. solution)  0.6% by weight Water 82.9% by weight

The different compounds prepared in Example 1 were individuallydissolved in ethanol (3 ml) at a concentration to release a total amountof 0.135 mmol of the fragrance and then dispersed in the above describedfabric softening surfactant emulsion (5.40 g). The samples were shakenand left standing overnight.

In a beaker, the fabric softening surfactant emulsion containing thecompound of formula (I) (2.60 g) was diluted with demineralised cold tapwater (600 g) and one cotton sheet (EMPA cotton test cloth Nr. 221,origin: Eidgenossische Materialprüfanstalt (EMPA), pre-washed with anunperfumed detergent powder and cut to ca. 12×12 cm sheets) was added toeach beaker. The sheet was manually stirred for 3 min, left standing for2 min, then wrung out by hand and line-dried for 1 or 3 days. As areference sample, the prior art compound3-(dodecylthio)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone(described as Example 4a in WO 03/049666) was prepared and treated inthe same way as described above. All measurements were performed atleast twice.

One dry cotton sheet was put into a headspace sampling cell (internalvolume ca. 160 ml), thermostatted at 25° C. and exposed to a constantair flow (200 ml/min), respectively. The air was filtered through activecharcoal and aspirated through a saturated solution of NaCl,corresponding to a constant humidity of ca. 75%. During 15 min, thevolatiles were adsorbed onto a waste Tenax® cartridge, then during 15min onto a clean Tenax® cartridge. The sampling was repeated 7 timesevery 60 min (45 min trapping on the waste cartridge and 15 min on aclean cartridge); the waste cartridges were discarded. The cartridgeswith the volatiles were thermally desorbed on a Perkin Elmer TurboMatrixATD desorber coupled to an Agilent Technologies 7890A GC System equippedwith a HP-1 capillary column (30 m, i.d. 0.32 mm, film 0.25 μm) and aflame ionization detector (FID). The volatiles were analyzed using atemperature gradient from 60° C. to 200° C. at 15° C./min. Headspaceconcentrations (in ng/1 of air) were obtained by external standardcalibration with different concentrations of the delta-damascone to beliberated. The headspace concentrations measured after 150 min ofsampling above the dry cotton sheets are listed in the tables below.

TABLE Average headspace concentrations of delta-damascone released fromthe compounds of formula (I) as prepared in Example 1 and from prior art3-(dodecylthio)-1-(2,6,6-trimethyl- 3-cyclohexen-1-yl)-1-butanone(described as Example 4a in WO 03/049666) in a fabric softenerapplication after drying for 1 day and sampling for 150 min. Amount ofFactor of α,β-unsaturated increase ketone, aldehyde with respect ornitrile released to the prior- Compound from [ng/l] art reference Priorart 24.2 1.0 (WO 03/049666) Example 1 xlviii 51.2 2.0 Example 1 xxiv62.9 2.6 Example 1 xxiii 82.8 3.4

TABLE Average headspace concentrations of delta-damascone released fromthe compounds of formula (I) as prepared in Example 1 and from prior art3-(dodecylthio)-1-(2,6,6-trimethyl- 3-cyclohexen-l-yl)-1-butanone(described as Example 4a in WO 03/049666) in a fabric softenerapplication after drying for 3 days and sampling for 150 min. Amount ofFactor of α,β-unsaturated increase ketone, aldehyde with respect ornitrile released to the prior- Compound from [ng/l] art reference Priorart 113.2 1.0 (WO 03/049666) Example 1 xv 130.6 1.2 Example 1 xxxviii132.0 1.2 Example 1 i 190.3 1.7 Example 1 v 207.6 1.8 Example 1 xxiii207.9 1.8 Example 1 xlvii 233.0 2.1 Example 1 xxvii 250.1 2.2 Example 1xlviii 256.1 2.3 Example 1 iv 277.4 2.5

The data show that the compounds of formula (I) as prepared in Example 1release considerably more delta-damascone in a fabric softenerapplication after 1 day and 3 days than the prior art3-(dodecylthio)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone(described as Example 4a in WO 03/049666).

Example 3 Performance of a Softener Base Comprising an Invention'sCompound of Formula (I) as Compared to the Unmodified α,β-UnsaturatedKetone, Aldehyde or Nitrile to be Released

The liberation of an α,β-unsaturated ketone, aldehyde or nitrile fromthe present invention's compounds of formula (I) was tested in a fabricsoftening surfactant emulsion as described above in Example 2. As areference sample, a solution containing an equimolar amount ofunmodified α,β-unsaturated ketone, aldehyde or nitrile to be liberatedfrom the compounds of formula (I) was added to a sample of the fabricsoftening surfactant emulsion and was treated as described above inExample 2. All measurements were performed at least twice. The headspaceconcentrations measured after 150 min of sampling above the dry cottonsheets are listed in the tables below and compared to the headspaceconcentrations of the corresponding unmodified α,β-unsaturated ketone,aldehyde or nitrile to be released from the compounds of formula (I)used as the reference.

TABLE Average headspace concentrations of α,β-unsaturated ketones,aldehydes or nitriles released from the compounds of formula (I) asprepared in Example 1 and of the corresponding unmodifiedα,β-unsaturated ketone, aldehyde or nitrile in a fabric softenerapplication after drying for 1 day and sampling for 150 min. Amount ofAmount of unmodified Factor of α,β-unsaturated α,β-unsaturated increaseketone, aldehyde ketone, aldehyde with respect Compound or nitrilereleased or nitrile (reference) to the from [ng/l] [ng/l] referenceExample 1 ix 11.9 1.7 7.0 Example 1 xiii 25.3 1.7 14.9 Example 1 iv 20.41.7 12.0 Example 1 vi 11.0 1.7 6.5 Example 1 xxvii 20.2 1.7 11.9 Example1 xliii 12.8 1.7 7.5 Example 1 xix 8.1 1.7 4.8 Example 1 xx 6.3 1.7 3.7Example 1 xxi 13.4 1.7 7.9 Example 1 xxii 22.3 1.7 13.1 Example 1 vii9.3 1.4 6.6 Example 1 xxxvi 3.4 1.0 3.4 Example 1 xxix 1.7 0.3 5.7Example 1 xxviii 28.0 0.1* 280.0 Example 1 ii 40.4 9.3 4.3 Example 1xxxiii 15.7 11.1 1.4 Example 1 iii 15.1 11.1 1.4 Example 1 xxxii 35.70.1* 357.0 *no compound was detected and a value of 0.1 ng/l was takenas the minimum of detection.

TABLE Average headspace concentrations of α,β-unsaturated ketones,aldehydes or nitriles released from the compounds of formula (I) asprepared in Example 1 and of the corresponding unmodifiedα,β-unsaturated ketone, aldehyde or nitrile in a fabric softenerapplication after drying for 3 days and sampling for 150 min. Amount ofAmount of unmodified Factor of α,β-unsaturated α,β-unsaturated increaseketone, aldehyde ketone, aldehyde with respect Compound or nitrilereleased or nitrile (reference) to the from [ng/l] [ng/l] referenceExample 1 xi 10.6 1.2 8.8 Example 1 xvi 44.4 1.2 37.0 Example 1 xvii33.5 1.2 27.9 Example 1 vi 83.8 1.2 69.8 Example 1 x 27.4 1.2 22.8Example 1 xxxix 20.2 1.2 16.8 Example 1 xxv 80.5 1.2 67.1 Example 1 xxvi104.5 1.2 87.1 Example 1 xli 54.4 1.2 45.3 Example 1 xlii 17.7 1.2 14.8Example 1 xlix 48.6 1.2 40.5 Example 1 xxi 63.2 1.2 52.7 Example 1 xl93.4 1.2 77.8 Example 1 xiv 73.7 1.2 61.4

The data show that the compounds of formula (I) as prepared in Example 1release considerably more α,β-unsaturated ketone, aldehyde or nitrile ina fabric softener application after 1 day and 3 days than the unmodifiedα,β-unsaturated ketone, aldehyde or nitrile reference sample.

Example 4 Performance of an all Purpose Cleaner Comprising anInvention's Compound of Formula (I)

The use as perfuming ingredient of the present invention's compounds offormula (I) has been tested in an all purpose surface cleaner (APC). AnAPC base with the following final composition has been prepared:

Neodol ® 91-8 (origin: Shell Chemicals) 5.0% by weight Marlon ® A 375(origin: Hüls AG) 4.0% by weight Sodium cumolsulphonate 2.0% by weightKathon ® CG (origin: Rohm and Haas) 0.2% by weight Water 88.8% byweight 

One of the invention's compounds of formula (I) was weighed into the APCbase (1 ml) at a concentration to release a total amount of 0.012 mmolof the fragrance. Then the sample was diluted with demineralized tapwater (9 ml). Another sample containing the unmodified α,β-unsaturatedketone, aldehyde or nitrile to be released (0.3 mmol) instead of theinvention's compound of formula (I) was prepared in the same way as thereference. The samples were shaken and then deposited as a film onto aporous ceramic plate (ca. 5×10 cm) by carefully pipetting 0.75 ml of thediluted samples onto the surface of the substrate. The samples were thencovered with a ca. 2.5.1 crystallizing dish and left standing at roomtemperature. After one day, the substrates were placed inside aheadspace sampling cell (ca. 625 ml) and exposed to a constant air flowof ca. 200 ml/min. The air was filtered through active charcoal andaspirated through a saturated solution of NaCl (to ensure a constanthumidity of the air of ca. 75%). During 135 min the headspace system wasleft equilibrating, and then the volatiles were adsorbed during 15minutes on a clean Tenax® cartridge. The cartridges were desorbed andanalyzed as described in Example 2. All measurements were performed atleast twice.

The headspace concentrations measured after 150 min of sampling abovethe porous ceramic plate are listed in the table below and compared tothe headspace concentrations of the corresponding unmodifiedα,β-unsaturated ketone, aldehyde or nitrile to be released from thecompounds of formula (I) used as the reference.

TABLE Average headspace concentrations of α,β-unsaturated ketones,aldehydes or nitriles released from the compounds of formula (I) asprepared in Example 1 and of the corresponding unmodifiedα,β-unsaturated ketone, aldehyde or nitrile in an all purpose cleanerapplication after 1 day and sampling for 150 min. Amount of Amount ofunmodified Factor of α,β-unsaturated α,β-unsaturated increase ketone,aldehyde ketone, aldehyde with respect Compound or nitrile released ornitrile (reference) to the from [ng/l] [ng/l] reference Prior art 16.013.7 1.2 (WO 03/049666) Example 1 xxv 21.6 13.7 1.6 Example 1 xxvii 26.113.7 1.9 Example 1 xxiii 53.9 13.7 3.9 Example 1 xxi 39.4 13.7 2.8

The data show that the compounds of formula (I) as prepared in Example 1release considerably more α,β-unsaturated ketone, aldehyde or nitrile ina fabric softener application after 1 day and 3 days than the unmodifiedα,β-unsaturated ketone, aldehyde or nitrile or the prior art3-(dodecylthio)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone(described as Example 4a in WO 03/049666).

What is claimed is:
 1. A method to confer, enhance, improve or modifythe odor properties of a perfuming composition or of a perfumed article,which method comprises adding to said composition or article aneffective amount of at least a compound of formula (I):

wherein: a) m represents an integer from 1 to 2; b) Pro represents ahydrogen atom or is a group of the formulae

in which formulae the wavy line indicates the location of the bondbetween said Pro and the S atom, the dotted lines represent a single ordouble bond, R⁷ indicating a hydrogen atom or a methyl group; and withthe proviso that at least one of the Pro groups is of the formulae (P-1)to (P-16) as defined hereinabove; c) X represents an oxygen atom; d) Rrepresents a CH(Me), CH₂, CH₂CH₂, CH₂CH₂CH₂, CH(Me)CH₂, CH(CH₂COOH) orCH(CH₂COOM) group, M being an alkaline metal cation; and e) G representsa sodium or potassium cation or a Si(Me)₃ group.
 2. The method asrecited in claim 1, wherein said group Pro is a group of the formulae(P-1), (P-2), (P-3), (P-4), (P-5), (P-6), or (P-7).
 3. The method asrecited in claim 1, wherein said m is
 1. 4. The method as recited inclaim 1 wherein said compound comprises a compound of formula

wherein Pro and G have the meaning indicated in claim 1, n is 1 or 2,and R⁸ represents a hydrogen atom or a methyl group or a CH₂COOH or aCH₂COOM group, with M being an alkaline metal cation or an ammoniumcation.
 5. A perfuming composition comprising as a perfuming ingredientto confer, enhance, improve or modify the odor properties of a perfumedarticle, comprising: a) as perfuming ingredient, at least one compoundof formula (I) as defined in claim 1; b) at least one ingredientselected from the group consisting of a perfumery carrier and aperfumery base; and c) optionally, at least one perfumery adjuvant.
 6. Aperfuming consumer product which comprises i) as perfuming ingredient,at least one compound of formula (I) as defined in claim 1; and ii) aperfumery consumer base.
 7. A perfuming consumer product according toclaim 6, characterized in that the perfumery consumer base is a fineperfume, a cologne, an after-shave lotion, a liquid or solid detergent,a fabric softener, a fabric refresher, an ironing water, a paper, ableach, a shampoo, a coloring preparation, a hair spray, a vanishingcream, a deodorant or antiperspirant, a perfumed soap, shower or bathmousse, oil or gel, a hygiene product, an air freshener, a “ready touse” powdered air freshener, a wipe, a dish detergent or hard-surfacedetergent.
 8. The method as recited in claim 1, wherein said group Prois a group of the formulae (P-1), (P-2), (P-3), (P-4), (P-5), (P-6),(P-7), (P-8), (P-9), (P-10) or (P-11).
 9. The method as recited in claim1, wherein said group Pro is a damascone, ionone, beta-damascenone,1-(5,5- or 3,3-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one, carvone,1-(2,2,3,6-tetramethyl-1-cyclohexyl)-2-buten-1-one,4-(2,2,3,6-tetramethyl-1-cyclohexyl)-3-buten-2-one, or citral.
 10. Themethod as recited in claim 1, wherein the compound of formula (I) isadded in a perfuming composition that also include at least oneingredient selected from the group consisting of a perfumery carrier anda perfumery base; and optionally, at least one perfumery adjuvant. 11.The method as recited in claim 1, wherein the compound of formula (I) isadded as perfuming ingredient to a perfuming consumer product thatcontains a perfuming consumer base.
 12. The method as recited in claim11 wherein the perfumery consumer base is a fine perfume, a cologne, anafter-shave lotion, a liquid or solid detergent, a fabric softener, afabric refresher, an ironing water, a paper, a bleach, a shampoo, acoloring preparation, a hair spray, a vanishing cream, a deodorant orantiperspirant, a perfumed soap, shower or bath mousse, oil or gel, ahygiene product, an air freshener, a “ready to use” powdered airfreshener, a wipe, a dish detergent or hard-surface detergent.